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In this contribution we demonstrate doping of graphene by uncharged dibenzyl viologen (DBV0). Deposited electrochemically on chemical vapor deposited (CVD) graphene on SiO2, DBV0 forms a water-insoluble self-assembled molecular network, in contrast to water-soluble monocationic DBV˙+. The phase formation at the molecular scale is revealed by scanning tunneling microscopy (STM) and atomic force microscopy (AFM). The doping efficiency is characterized by a combination of Raman spectroscopy and Kelvin probe force microscopy (KPFM). The Raman mapping of the G-band of the DBV0 adlayer on top of CVD graphene on SiO2 shows an apparent red shift compared to the unmodified analogue indicating an n-doping effect. This observation is in line with the KPFM results of which the measured contact potential difference (CPD) displays a positive shift compared to that of the pristine graphene.

ispartof: JOURNAL OF PHYSICAL CHEMISTRY C vol:125 issue:39 pages:21624-21634 status: published

ispartof: JOURNAL OF PHYSICAL CHEMISTRY C vol:126 issue:25 pages:10494-10505 status: published

A novel fluorinated soft thermoplastic elastomer (sTPE) for microfluidics is presented. It allows the rapid fabrication of microfluidic devices through a 30‐second hot embossing cycle at 220°C followed by self‐sealing through simple conformal contact at room temperature, or with baking. The material shows high chemical resistance, particularly in comparison to polydimethylsiloxane (PDMS), to many common organic solvents and can be rapidly micropatterned with high fidelity using a variety of microfluidic master molds thanks to its low mechanical stiffness. Self‐sealing of the material is reversible and withstands pressures of up to 2.8 bar with room temperature sealing and four bar with baking at 185°C for 2 hours. The elastomeric, transparent sTPE exhibits material characteristics that make it suited for use as a microreactor, such as low absorption, surface roughness and oxygen permeability, while also allowing a facile and scalable fabrication process. Modular microfluidic devices, leveraging the fast and reversible room temperature self‐sealing, are demonstrated for the generation of water droplets in a toluene continuous phase using T‐junctions of variable size. The sTPE offers an alternative to common microfluidic materials, overcoming some of their key drawbacks, and giving scope for low‐cost and high‐throughput devices for flow chemistry applications.

Controlled chemical functionalization of graphite’s outer surface layers into photocatalytically oxidized graphite (POG) is reported. POG can be easily prepared via a UV-driven process using titanium dioxide photocatalyst in molecular oxygen and water vapor at relatively low temperature. The photo-oxidation offers a mild and highly controllable process, providing a chemically tailored POG surface with moderate oxidation degree. Raman spectroscopy is used to directly track the transformation of planar sp2-hybridized carbon to oxygenated sp3-hybridized chemical functions. Covalent carbon-oxygen bonding at the graphite surface upon oxidation is confirmed by XPS. This vapor-phase process in absence of hazardous liquid chemicals causes oxygen-functionalized and thermally stable POG with an oxygen content up to 14 wt%, suggesting it to be useful for electrocatalysis. Oxidation can be performed with the photocatalyst in direct contact with graphite or mounted at a distance (remote mode). This titanium dioxide-based photocatalytic oxidation is also effective on refractory highly oriented pyrolytic graphite (HOPG). HRSEM and AFM reveal the existence of differently sized surface blisters on natural graphite and HOPG following oxidation. Addition of nitric oxide to the gas mixture accelerates the photoreaction and promptly leads to graphite surface pits and edge erosion due to excessive oxidative strength.

Oxidative modification of graphene-based materials is an attractive route to functional materials. The use of strong oxidants to achieve surface modification of the carbon often leads to poor uniformity and limited reproducibility. Photocatalytic oxidation is a milder method. In this work, graphite is surface oxidized using an anatase thin photocatalytic film with a thickness of 22.5 nm facing the graphite surface to be oxidized. The high UV light transparency (95%) of the supported titania film simplified the experimental setup. The titania thin film was prepared using atomic layer deposition (ALD). Excellent oxidation uniformity and reaction reproducibility are achieved. By avoiding the use of chemical reagents there is no chemical contamination. Graphite photo-oxidation with the titania film prepared with ALD is much faster than with a powdery photocatalyst. The photocatalytic process runs efficiently with air containing water vapor. High resolution scanning electron microscopy (HRSEM), Raman and X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) confirmed the formation of hydroxyl, epoxy and carbonyl functional groups. ALD is a suitable method for thin film preparation rendering this photocatalytic process suitable for scale-up and automation. Photocatalytically oxidized graphite (POG) electrodes are a potential application.

Carbocatalysis holds a privileged position as a sustainable alternative to metal-based catalysis. While the focus in solution-based catalytic processes generally lies on how the heterogeneous catalyst affects the solution composition, more attention has recently been given to the analysis of the carbon material itself. Various outstanding surface characterisation techniques, efficient in assessing the catalyst on-surface composition, are now available. These include high-resolution imaging tools such as scanning tunneling microscopy (STM), capable of bringing new insights into the processes determining rate and selectivity effects induced by carbocatalysts. In this regard, the use of self-assembly on graphite as a strategy to direct the outcome of chemical reactions has already shown great potential. This promising approach gives the scientific community the exciting prospect of rationalising selectivity in carbocatalysis with pristine graphite by linking in-solution and on-surface composition.

Chirality in two dimensions (2D) has attracted increasing attention with regard to interesting fundamental aspects as well as potential applications. This article reports several aspects of supramolecular chirality control as exemplified by self-assembled monolayer networks (SAMNs) formed by a class of chiral building blocks consisting of a triangular conjugated core and alkoxy chains on the periphery. It highlights 2D chirality induction phenomena through a classic "sergeants-and-soldiers" mechanism, in which the inducer is incorporated into a network component, as well as through a "supramolecular host-guest" mechanism, in which the inducer is entrapped in the porous space, leading to counterintuitive chirality reversal. Stereochemical control can be extended to three dimensions too, based on interlayer hydrogen bonding of the same class of building blocks bearing hydroxy groups, exhibiting diastereospecific bilayer formation at both single molecule level and supramolecular level arising from orientation between the top and bottom layers. Finally, we showcase that homochiral SAMNs can also be used as templates for the grafting of in situ generated aryl radicals, by covalent bond formation to the basal graphitic surface, thereby yielding topologically chiral functionalized graphite, and thus extending the potential of chiral SAMNs.

ispartof: JOURNAL OF PHYSICAL CHEMISTRY C vol:126 issue:14 pages:6413-6419 status: published

Covalent functionalization of graphene (CFG) has shown attractive advantages in tuning the electronic, mechanical, optical, and thermal properties of graphene. However, facile, large-scale, controllable, and highly efficient CFG remains challenging and often involves highly reactive and volatile compounds, requiring complex control of the reaction conditions. Here, a diazonium-based grafting ink consisting of only two components, i.e., an aryl diazonium salt and the solvent dimethyl sulfoxide (DMSO) is presented. The efficient functionalization is attributed to the combination of the solvation of the diazonium cations by DMSO and n-doping of graphene by DMSO, thereby promoting electron transfer (ET) from graphene to the diazonium cations, resulting in the generation of aryl radicals which subsequently react with the graphene. The grafting density of CFG is controlled by the reaction time and very high levels of functionalization, up to the failing of the Tuinstra-Koenig (T-K) relation, while the functionalization layer remains at monolayer height. The grafting ink, effective for days at room temperature, can be used at ambient conditions and renders the patterning CFG by direct writing as easy as writing on paper. In combination with thermal sample treatment, reversible functionalization is possible by subsequent writing/erasing cycles. ispartof: ADVANCED SCIENCE vol:9 issue:19 ispartof: location:Germany status: published

Reported here is a molecular dipole that self‐assembles into highly ordered patterns at the liquid‐solid interface, and it can be switched at room temperature between a bright and a dark state at the single‐molecule level. Using a scanning tunneling microscope (STM) under suitable bias conditions, binary information can be written at a density of up to 41 Tb cm−2 (256 Tb/in2). The written information is stable during reading at room temperature, but it can also be erased at will, instantly, by proper choice of tunneling conditions. DFT calculations indicate that the contrast and switching mechanism originate from the stacking sequence of the molecular dipole, which is reoriented by the electric field between the tip and substrate.

Silver nanowires have attracted considerable attention as subdiffraction limited diameter waveguides in a variety of applications including cell endoscopy and photonic integrated circuitry. Optical signal transport occurs by coupling light into propagating surface plasmons, which scatter back into light further along the wire. However, these interconversions only occur efficiently at wire ends, or at defects along the wire, which are not controlled during synthesis. Here, we overcome this limitation, demonstrating the visible laser light-induced fabrication of gold nanostructures at desired positions on silver nanowires, and their utility as efficient in/out coupling points for light. The gold nanostructures grow via plasmon-induced reduction of Au(III) and are shown to be excellent "hotspots" for surface-enhanced Raman scattering. ispartof: NANO LETTERS vol:20 issue:4 pages:2460-2467 ispartof: location:United States status: published

Synthetic two-dimensional polymers (2DPs) obtained from well-defined monomers via bottom-up fabrication strategies are promising materials that can extend the realm of inorganic 2D materials. The on-surface synthesis of such 2DPs is particularly popular, however the pathway complexity in the growth of such films formed on solid surfaces is poorly understood. In this contribution, we present a straightforward experimental protocol which allows the synthesis of large-area, defect-free 2DPs based on boroxine linkages at room temperature. We focus on unravelling the multiple pathways available to the polymerizing system for the spatial extension of the covalent bonds. Besides the anticipated 2DP, the system can evolve into self-assembled monolayers of partially fused monodisperse reaction products that are difficult to isolate by conventional synthetic methods or remain in the monomeric state. The access to each pathway can be controlled via monomer concentration and the choice of the solvent. Most importantly, the unpolymerized systems do not evolve into the corresponding 2DP upon annealing, indicating the presence of strong kinetic traps. Using high-resolution scanning tunneling microscopy, we show reversibility in the polymerization process where the attachment and the detachment of monomers to 2DP crystallites could be monitored as a function of time. Finally, we show that the way the 2DP grows depends on the choice of the solvent. Using UV-vis absorption and emission spectroscopy, we reveal that the dominant pathway for 2DP growth is via in-plane self-condensation of the monomers, whereas in the case of an aprotic solvent, the favored growth mode is via π stacking of the monomers. ispartof: ACS NANO vol:14 issue:2 pages:2354-2365 ispartof: location:United States status: published

Halogen bonds, which provide an intermolecular interaction with moderate strength and high directionality, have emerged as a promising tool in the repertoire of non‐covalent interactions. In this review, we provide a survey of the literature where halogen bonding was used for the fabrication of supramolecular networks on solid surfaces. The definitions of, and the distinction between halogen bonding and halogen‐halogen interactions are provided. Self‐assembled networks formed at the solution/solid interface and at the vacuum‐solid interface, stabilized in part by halogen bonding, are discussed. Besides the broad classification based on the interface at which the systems are studied, the systems are categorized further as those sustained by halogen‐halogen and halogen‐heteroatom contacts., A survey of systems in which halogen bonding was used for the fabrication of supramolecular networks on solid surfaces is reported. Self‐assembled networks formed at the solution/solid interface and at the vacuum/solid interface, stabilized in part by halogen bonding, are discussed.

The chemistry of carbon surfaces has regained traction in recent years in view of its applicability towards covalent modification of a variety of (2D) materials. A general requisite is the formation of a dense and well-defined monolayer of aryl groups covalently bound to the surface. Given the use of reactive chemistries however, it is often not easy to achieve precise control over the monolayer growth while maintaining high grafting densities. Here we present a straightforward experimental protocol for the fabrication of well-defined covalent monolayers onto the surface of graphite. Using a combination of surface analytical tools, we demonstrate that the ascorbic acid mediated dediazoniation of aryldiazonium salts leads to self-limiting growth of monolayers with high grafting densities. The aryl radicals preferentially attach to the basal plane of the substrate and once the surface is covered with a covalent monolayer, the surface reaction does not proceed further to an appreciable extent. The layer thickness of the covalent films was measured using atomic force microscopy whereas the grafting efficiencies were assessed using Raman spectroscopy. The chemical composition of the grafted films was studied using X-ray photoelectron spectroscopy whereas scanning tunneling microscopy provided nanometer scale insight into the structure of the covalent films. Mechanistic aspects of the process are also discussed. The self-terminating chemistry described here is a new addition to the synthetic armory for covalent modification of materials and sets a strong foundation for achieving precise nanoscale control over the covalent functionalization process. ispartof: NANOSCALE vol:12 issue:36 pages:18782-18789 ispartof: location:England status: published

We report on the epitaxial growth of photoresponsive alkyl-substituted azobenzene fibres on top of uniaxially oriented polyethylene (PE) films. In these fibres, the alkyl chains are oriented parallel with regard to the drawing direction of PE, whereas the azobenzene moieties pack into a roughly 60° angle. The bilayer films act as a light responsive actuator generating an actuation stress of about 3 MPa.

We herein report a unique example of on-surface adaptive self-assembly. A pentagon-shaped macrocycle, cyclic [5]meta-phenyleneacetylene [5]CMPA, is trapped by the adaptive supramolecular network formed by an isosceles triangular molecule, alkoxy substituted dehydrobenzo[14]annulene [14]ISODBA at the liquid/graphite interface, leading to a highly ordered and large-area bicomponent self-assembled molecular network (SAMN), as revealed by scanning tunneling microscopy (STM).

The fabrication of highly ordered nanostructured surfaces is desirable in supramolecular chemistry and envisaged to bolster advances in heterogeneous catalysis and microelectronic applications. Here, we report on a novel set of alkylated doubleN,N′-bis(n-alkyl)-naphthalenediimides (NDIs) for the functionalization of highly oriented pyrolytic graphite (HOPG) with precise double lamellar morphologies. A detailed analysis of the two-dimensional (2D) self-assembled monolayers by scanning tunneling microscopy (STM) reveals that the structural repeating unit of the double lamellae is tuned precisely by the length of the alkyl chain that is connecting the NDI units. However, the expected odd-even effect is disturbed within the monolayers of a series of homologues. In contrast, a clear odd-even effect is observed for the melting temperatures of the respective bulk materials. Small-angle X-ray scattering reveals that these bulk materials exhibit nanophase-separated lamellar phases with domain spacings that are slightly larger than the repeating units of the double lamellar structures formed on the HOPG surface. The discrepancy is assigned to a partial desorption of the alkyl spacer from the HOPG surface, which becomes more pronounced when increasing its length. Our findings suggest that this lengthening increases the conformational freedom of the molecules on the surface while retaining a double lamellar morphology.

We report the formation of nanobubbles on graphene with a radius of the order of 1 nm, using ultralow energy implantation of noble gas ions (He, Ne, Ar) into graphene grown on a Pt(111) surface. We show that the universal scaling of the aspect ratio, which has previously been established for larger bubbles, breaks down when the bubble radius approaches 1 nm, resulting in much larger aspect ratios. Moreover, we observe that the bubble stability and aspect ratio depend on the substrate onto which the graphene is grown (bubbles are stable for Pt but not for Cu) and trapped element. We interpret these dependencies in terms of the atomic compressibility of the noble gas as well as of the adhesion energies between graphene, the substrate, and trapped atoms. ispartof: NANO LETTERS vol:21 issue:19 pages:8103-8110 ispartof: location:United States status: published

In this paper, we give an overview of different chemical modifications that can be done on the surface of two-dimensional (2D) layered materials. We place emphasis on the diversity of reactions that have been proposed and are now available to surface scientists working in 2D materials field. Using mainly, but not exclusively, MoS2 as example, reactions involving covalent and non-covalent interactions are discussed.

The integration of graphene, and more broadly two-dimensional materials, into devices and hybrid materials often requires the deposition of thin films on their usually inert surface. As a result, strategies for the introduction of surface reactive sites have been developed but currently pose a dilemma between robustness and preservation of the graphene properties. A method is reported here for covalently modifying graphitic surfaces, introducing functional groups that act as reactive sites for the growth of high quality dielectric layers. Aryl diazonium species containing tri-methoxy groups are covalently bonded (grafted) to highly oriented pyrolytic graphite (HOPG) and graphene, acting as seeding species for atomic layer deposition (ALD) of Al2O3, a high-κ dielectric material. A smooth and uniform dielectric film growth is confirmed by scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrical measurements. Raman spectroscopy showed that the aryl groups gradually detach from the graphitic surface during the Al2O3 ALD process at 150 °C, with the surface reverting back to the original sp2-hybridized state and without damaging the dielectric layer. Thus, the grafted aryl groups can act as a sacrificial seeding layer after healing the defects of the graphitic surface with annealing treatment.

Self-sorting of multiple building blocks for correctly positioning molecules through orthogonal recognition is a promising strategy for construction of a hierarchical self-assembled molecular network (SAMN) on a surface. Herein we report that a trigonal molecule, dehydrobenzo[12]annulene (DBA) derivative having three tetradecyloxy chains and three hydroxy groups in an alternating manner, forms hierarchical triangular clusters of different sizes ranging from 2.4 to 16.4 nm, consisting of 3 to 78 molecules, respectively, at the liquid/graphite interface. The key is the dynamic combination of three different conformational states, which is solvent and concentration dependent. The present knowledge extends design strategies for production of sophisticated hierarchical SAMNs using a single component at the liquid/solid interface., Self-sorting of multiple building blocks for correctly positioning molecules through orthogonal recognition is a promising strategy for construction of a hierarchical self-assembled molecular network (SAMN) on a surface.

Control over polymorph formation in the crystallization of organic molecules remains a huge scientific challenge. Now, preferential formation is presented of one polymorph, formed by chiral molecules, in controlled two-dimensional (2D) nanoconfinement conditions at a liquid-solid interface. So-called nanocorrals to control concomitant polymorph formation were created in situ via a nanoshaving protocol at the interface between 1-phenyloctane and covalently modified highly-oriented pyrolytic graphite (HOPG). The preferentially formed polymorphs, which were less stable in the large-scale monolayers, could be selected simply by varying the orientation of the square nanocorrals with respect to the HOPG lattice. ispartof: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION vol:58 issue:37 pages:12964-12968 ispartof: location:Germany status: published

The impact of lateral confinement on the 2D self-assembly of a normal alkane is investigated via scanning tunneling microscopy-based nanoshaving on covalently modified graphite surfaces. Physical constraints placed on the confined assemblies lead to geometric frustration, which is shown to be released via a suppression of the lamellar order. This result is explained on the basis of competing enthalpic contributions from molecule–molecule and molecule–substrate interactions and is corroborated by a simple coarse-grain model. Furthermore, a pronounced molecular alignment effect results from the in situ nanoshaving procedure.

Scanning tunnelling microscope observations at the 1-phenyloctane/graphite interface reveal how chiral structural information at the molecular level is transferred and expressed structurally at the 2D supramolecular level for a porous system. The chirality of self-assembled molecular networks formed by chiral dehydrobenzo[12]annulene (cDBA) derivatives having three chiral chains and three achiral chains, alternatingly, is compared with those of cDBAs having six chiral chains reported previously. While for all cDBAs homochiral surfaces are formed, their handedness is not simply a reflection of the absolute configuration of the stereogenic centres. Both the number of stereogenic centres as well as the length of the achiral chains determine the supramolecular handedness, providing a deep insight into the supramolecular chirality induction mechanisms at play. Moreover, these cDBAs act to induce chirality in porous networks formed by achiral DBAs. ispartof: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION vol:58 issue:23 pages:7733-7738 ispartof: location:Germany status: published

By using a novel protocol to spatially confine molecules in well-defined small 2D areas, the so-called nanocorrals, we show using scanning tunneling microscopy (STM) how this kind of confinement affects self-assembled molecular network (SAMN) formation at a liquid-solid interface. The 2D lateral confinement, imposed by the size of the nanocorrals, has a clear impact on the phase selectivity of a molecule that can form both low-density and high-density SAMNs, the high-density phase being promoted by the confinement. ispartof: CHEMICAL COMMUNICATIONS vol:55 issue:15 pages:2226-2229 ispartof: location:England status: published

Self-assembled molecular networks (SAMNs) on surfaces evoke a lot of interest, both from a fundamental as well as application point of view. When formed at the liquid–solid interface, precise control over different polymorphs can be achieved by simply adjusting the concentration of molecular building blocks in solution. Significant influence of solute concentration on self-assembly behavior has been observed, whether the self-assembly behavior is controlled by either van der Waals forces or hydrogen bonding interactions. In both cases, high- and low-density supramolecular networks have been observed at high and low solute concentrations, respectively. In contrast to this “concentration-in-control” self-assembly concept here we report an atypical concentration dependent self-assembly behavior at a solution–solid interface. At the interface between heptanoic acid (HA) and highly oriented pyrolytic graphite (HOPG), we show, using scanning tunneling microscopy (STM), the formation of a low-density porous network at high solute concentrations, and a high-density compact network at low solute concentrations. This intriguing inverse concentration dependent self-assembly behavior has been attributed to the preaggregation of solute molecules in the heptanoic acid solution as revealed by UV-vis spectroscopy. The observed results have been correlated to the molecular density of self-assembled monolayers attained at the HA/HOPG interface., Surprise! against expectations, increasing (decreasing) the solute concentration leads to the formation of a low-density (high-density) self-assembled molecular network at the liquid–solid interface.

The chemical patterning of graphene is being pursued tenaciously due to exciting possibilities in electronics, catalysis, sensing, and photonics. Despite the intense efforts, spatially controlled, multifunctional covalent patterning of graphene has not been achieved. The lack of control originates from the inherently poor reactivity of the basal plane of graphene, which necessitates the use of harsh chemistries. Here, we demonstrate spatially resolved multicomponent covalent chemical patterning of single layer graphene using a facile and efficient method. Three different functional groups could be covalently attached to the basal plane in dense, well-defined patterns using a combination of lithography and a self-limiting variant of diazonium chemistry requiring no need for graphene activation. The layer thickness of the covalent films could be controlled down to 1 nm. This work provides a solid foundation for the fabrication of chemically patterned multifunctional graphene interfaces for device applications.

Chemical vapor deposition of metal-organic frameworks (MOF-CVD) will facilitate the integration of porous and crystalline coatings in electronic devices. In the two-step MOF-CVD process, a precursor layer is first deposited and subsequently converted to a MOF through exposure to linker vapor. We herein report the impact of different metal oxide and metalcone layers as precursors for zeolitic imidazolate framework ZIF-8 films. ispartof: DALTON TRANSACTIONS vol:50 issue:20 pages:6784-6788 ispartof: location:England status: published

A small percentage of an impurity was shown, via scanning tunneling microscopy, to drastically change the on-surface self-assembly behavior of an aromatic tetracarboxylic acid, by initiating the nucleation and growth of a different polymorph. Molecular modelling simulations were used to shed further light onto the dopant-controlled assembly behaviour. ispartof: CHEMICAL COMMUNICATIONS vol:57 issue:12 pages:1454-1457 ispartof: location:England status: published

The adsorption and self-assembly of n-alkanes on graphite not only find value in applications related to lubrication and surface passivation but are also of fundamental importance in the study of m...

We report the incorporation of substitutional Mn atoms in high-quality, epitaxial graphene on Cu(111), using ultralow-energy ion implantation. We characterize in detail the atomic structure of substitutional Mn in a single carbon vacancy and quantify its concentration. In particular, we are able to determine the position of substitutional Mn atoms with respect to the Moiré superstructure (i.e., local graphene-Cu stacking symmetry) and to the carbon sublattice; in the out-of-plane direction, substitutional Mn atoms are found to be slightly displaced toward the Cu surface, that is, effectively underneath the graphene layer. Regarding electronic properties, we show that graphene doped with substitutional Mn to a concentration of the order of 0.04%, with negligible structural disorder (other than the Mn substitution), retains the Dirac-like band structure of pristine graphene on Cu(111), making it an ideal system in which to study the interplay between local magnetic moments and Dirac electrons. Our work also establishes that ultralow-energy ion implantation is suited for substitutional magnetic doping of graphene. Given the flexibility, reproducibility, and scalability inherent to ion implantation, our work creates numerous opportunities for research on magnetic functionalization of graphene and other two-dimensional materials. PMID: 33596385 ispartof: ACS NANO vol:15 issue:3 pages:5449-5458 ispartof: location:United States status: published

Defects influence the properties of metal-organic frameworks (MOFs), such as their storage amount and the diffusion kinetics of gas molecules. However, the spatial distribution of defects is still poorly understood due to a lack of visualization methods. Here, we present a new method using nonlinear optics (NLO) that allows the visualization of defects within MOFs. ispartof: CHEMICAL COMMUNICATIONS vol:56 issue:87 pages:13331-13334 ispartof: location:England status: published

Metal–organic frameworks (MOFs) offer disruptive potential in micro- and optoelectronics because of the unique properties of these microporous materials. Nanoscale patterning is a fundamental step in the implementation of MOFs in miniaturized solid-state devices. Conventional MOF patterning methods suffer from low resolution and poorly defined pattern edges. Here, we demonstrate the resist-free, direct X-ray and electron-beam lithography of MOFs. This process avoids etching damage and contamination and leaves the porosity and crystallinity of the patterned MOFs intact. The resulting high-quality patterns have excellent sub-50-nm resolution, and approach the mesopore regime. The compatibility of X-ray and electron-beam lithography with existing micro- and nanofabrication processes will facilitate the integration of MOFs in miniaturized devices. The low dielectric constants and high porosity of MOFs are of interest for applications in electronics and sensors, but patterning techniques for these materials are in their infancy. Here, direct X-ray and electron-beam lithography at sub-50-nm resolution are reported that leave porosity and crystallinity intact.

Structural polymorphism is ubiquitous in physisorbed self-assembled monolayers formed at the solution–solid interface. One of the ways to influence network formation at this interface is to physically decouple the self-assembled monolayer from the underlying substrate thereby removing the influence of the substrate lattice, if any. Here we show a systematic exploration of self-assembly of a typical building block, namely 4-tetradecyloxybenzoic acid at the 1-phenyloctane–graphite interface in the presence and in the absence of a buffer layer formed by a long chain alkane, namely n-pentacontane. Using scanning tunneling microscopy (STM), three different structural polymorphs were identified for 4-tetradecyloxybenzoic acid at the 1-phenyloctane–graphite interface. Surprisingly, the same three structures were formed on top of the buffer layer, albeit at different concentrations. Systematic variation of experimental parameters did not lead to any new network in the presence of the buffer layer. We discovered that the self-assembly on top of the buffer layer allows better control over the nanoscale manipulation of the self-assembled networks. Using the influence of the STM tip, we could initiate the nucleation of small isolated domains of the benzoic acid on-command in a reproducible fashion. Such controlled nucleation experiments hold promise for studying fundamental processes inherent to the assembly process on surfaces. ispartof: Beilstein Journal Of Nanotechnology vol:11 issue:1 pages:1291-1302 ispartof: location:Germany status: Published online

Covalent functionalization of graphene is highly sought after, not only in view of the potential applications of the chemically modified material, but also because it brings fundamental insight into the chemistry of graphene. Thus, strategies that yield chemically modified graphene with densely grafted films of aryl groups via simple experimental protocols have been the focus of intense research. Here we report a mild, straightforward and efficient approach to graphene/graphite functionalization using iodide mediated reductive dediazoniation of aryldiazonium salts. The experimental protocol employs aqueous solutions of the reagents. The reaction proceeds rapidly at room temperature without the need of any environmental or electrochemical control. The covalently modified surfaces were characterized at the nanometer scale using a combination of complementary surface analytical techniques. The degree of covalent functionalization, and the morphology, as well as the thickness of the grafted films were studied at the molecular level using Raman spectroscopy and scanning probe microscopy, respectively. Furthermore, solution phase UV-Vis spectroscopy was employed to understand the mechanistic aspects. This work demonstrates a facile and scalable covalent modification method compatible for both bulk and monolayer functionalization of graphene. ispartof: NANOSCALE vol:12 issue:22 pages:11916-11926 ispartof: location:England status: published

Graphene, a single atomic layer of sp2 hybridized carbon, is a promising material for future devices due to its excellent optical and electrical properties. Nevertheless, for practical applications, it is essential to deposit patterned metals on graphene in the micro and nano-meter scale in order to inject electrodes or modify the 2D film electrical properties. However, conventional methods for depositing patterned metals such as lift-off or etching leave behind contamination. This contamination has been demonstrated to deteriorate the interesting properties of graphene such as its carrier mobility. Therefore, to fully exploit the unique properties of graphene, the controlled and nano-patterned deposition of metals on graphene films without the use of a sacrificial resist is of significant importance for graphene film functionalization and contact deposition. In this work, we demonstrate a practical and low-cost optical technique of direct deposition of metal nano-patterned structures without the need for a sacrificial lift-off resist. The technique relies on the laser induced reduction of metal ions on a graphene film. We demonstrate that this deposition is optically driven, and the resolution is limited only by the diffraction limit of the light source being used. Patterned metal features as small as 270 nm in diameter are deposited using light with a wavelength of 532 nm and a numerical aperture of 1.25. Deposition of different metals such as Au, Ag, Pd, Pb and Pt is shown. Additionally, change in the Fermi level of the graphene film through the nano-patterned metal is demonstrated through the electrical characterization of four probe field effect transistors. ispartof: NANOSCALE vol:12 issue:20 pages:11063-11069 ispartof: location:England status: published

ispartof: CHEMNANOMAT vol:6 issue:4 pages:550-559 status: published

The covalent functionalization of carbon-based materials through aryldiazonium chemistry has emerged as a powerful tool for physicochemical property modification. However, the characterization tech...

The self-assembly of an asymmetric perylene diimide (PDI) with a dove-tailed side chain is investigated after thermal annealing at various temperatures in solid-state. After annealing at low temperatures PDI dimers are formed through hydrogen bonding between the imide and carbonyl groups, together with π–stacking interactions leading to a helical packing of the molecules in supramolecular columnar structures. After annealing at higher temperatures a transformation into a layered organization with improved molecular order is observed. The driving force for this thermodynamically favorable reorganization and planarization of the PDI dimer is additional intermolecular hydrogen bonding between the carbonyl and aromatic H(Ar) that is also present in monolayers that are visualized by scanning tunneling microscopy. This study demonstrates the importance of hydrogen bonding on tuning the supramolecular organization of asymmetric PDI. Depending on the dominating interactions, a wide variety of complex supramolecular structures with unique properties can be initiated.

Engineering atomic structures at metal surfaces represents an important step in the development of novel nanomaterials and nanodevices, but relies predominantly on atomic/molecular beam epitaxy under ultrahigh vacuum conditions, where controlling the deposition processes remains challenging. By using solution-borne nanosized gold clusters as a precursor, here we develop a wet deposition protocol to the fabrication of atomically flat gold nanoislands, so as to utilize the dynamic exchange of surface-active molecules at the liquid-metal interface for manipulating the growth kinetics of ultrathin metallic nanostructures. While remarkable shape and size selection of gold nanoislands is observed, our experimental and theoretical investigations provide compelling evidences that organic adsorbates can impart a bias to the island orientation by preferred adsorption and alignment and intervene in the assembly and disassembly of adatom islands by complexing with Au adatoms. This approach offers a simple solution to regulate atomic layer growth of metals at ambient conditions., Ultrathin metallic films are most often fabricated by atomic or molecular beam epitaxy under ultrahigh vacuum conditions, where it is difficult to control deposition and growth. Here, the authors describe a wet deposition method, using solution-borne gold nanocluster precursors, to regulate growth of atomically flat gold nanoislands on a surface.

Through the incorporation of chiral and achiral poly(3-alkylthiophenes) (P3ATs) into a star-shaped system, a well-defined supramolecular organization is obtained lacking the unfavorable linear lamellar structure typically obtained for P3AT. Through the combination of a controlled chain-growth polymerization and efficient postpolymerization and click reactions, well-defined star-shaped P3ATs with a low dispersity of 1.1 were obtained. The combination of UV–vis, circular dichroism (CD), atomic force microscopy (AFM), and transmission electron microscopy (TEM) measurements showed the formation of a strong (chiral) supramolecular organization into fibers, different and stronger than those obtained with the linear P3ATs. The fact that the width of the fibers is in good agreement with the width of a single star-shaped P3AT excludes the formation of a linear lamellar structure. Furthermore, the particular supramolecular organization of the star-shaped polymers, which appears thanks to the precision polymer synth...

© 2018 American Chemical Society. Chemical and structural defects in otherwise pristine materials can result in either an improved or degraded material performance. Unfortunately, little is known about the role of these defects in complex hierarchical processes, such as self-assembly. Here, the influence of defective surfaces on physisorbed self-assembly occurring at liquid/solid interfaces is investigated. Covalently bound defects on graphite surfaces are generated by electrochemically activating diazonium cations. After creating the defective substrates, a solution containing self-assembling molecules was deposited on the surface. Subsequent scanning probe investigations expose how the chemisorbed molecular units can either be incorporated within a porous hexagonal network, or generate local perturbations in the form of partial or full desorption of the physisorbed molecules. Overall, the chemisorbed molecules alter the local energy landscape for self-assembly to isolate new molecular packing arrangements. With a single-molecule perspective, this work outlines how chemical defects contribute to the formation of metastable assemblies and their evolutionary pathways toward higher-symmetry networks. ispartof: JOURNAL OF PHYSICAL CHEMISTRY C vol:122 issue:42 pages:24046-24054 status: published

Two unprecedented porphyrin fused nanographene molecules, 1 and 2, have been synthesized by the Scholl reaction from tailor-made precursors based on benzo[m]tetraphene-substituted porphyrins. The chemical structures were validated by a combination of high-resolution matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (HR MALDI-TOF MS), IR and Raman spectroscopy, and scanning tunnelling microscopy (STM). The UV-vis-near infrared absorption spectroscopy of 1 and 2 demonstrated broad and largely red-shifted absorption spectra extending up to 1000 and 1400 nm, respectively, marking the significant extension of the π-conjugated systems. ispartof: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION vol:57 issue:35 pages:11233-11237 ispartof: location:Germany status: published

Understanding how molecules interact to form large-scale hierarchical structures on surfaces holds promise for building designer nanoscale constructs with defined chemical and physical properties. Here, we describe early advances in this field and highlight upcoming opportunities and challenges. Both direct intermolecular interactions and those that are mediated by coordinated metal centers or substrates are discussed. These interactions can be additive, but they can also interfere with each other, leading to new assemblies in which electrical potentials vary at distances much larger than those of typical chemical interactions. Earlier spectroscopic and surface measurements have provided partial information on such interfacial effects. In the interim, scanning probe microscopies have assumed defining roles in the field of molecular organization on surfaces, delivering deeper understanding of interactions, structures, and local potentials. Self-assembly is a key strategy to form extended structures on surfaces, advancing nanolithography into the chemical dimension and providing simultaneous control at multiple scales. In parallel, the emergence of graphene and the resulting impetus to explore 2D materials have broadened the field, as surface-confined reactions of molecular building blocks provide access to such materials as 2D polymers and graphene nanoribbons. In this Review, we describe recent advances and point out promising directions that will lead to even greater and more robust capabilities to exploit designer surfaces. ispartof: ACS NANO vol:12 issue:8 pages:7445-7481 ispartof: location:United States status: published

The noncovalent functionalization of surfaces has gained widespread interest in the scientific community, and it is progressively becoming an extremely productive research field offering brand new directions for both supramolecular and materials chemistry. As the end-groups often play a dominant role in the surface properties obtained, creating loops with end-groups only at the surface will lead to unexpected architectures and hence properties. Here we report the self-assembly of discrete block molecules-structures in-between block copolymers and liquid crystals-featuring oligodimethylsiloxanes (ODMS) end-capped with naphthalenediimides (NDIs) at the 1-phenyloctane/highly oriented pyrolytic graphite (1-PO/HOPG) interface. These structures produce unprecedented vertically nanophase-separated monolayers featuring NDI moieties that regularly arrange on the HOPG surface, while the highly dynamic ODMS segments form loops above them. Such arrangement is preserved upon drying and generates hydrophobic HOPG substrates in which the ODMS block length tunes the hydrophobicity. Thus, the exact structural fidelity of the discrete macromolecules allows for the correlation of nanoscopic organization with macroscopic properties of the self-assembled materials. We present a general strategy for tunable hydrophobic coatings on graphite based on molecularly combining crystalline aromatic moieties and immiscible oligodimethylsiloxanes. ispartof: CHEMISTRY OF MATERIALS vol:30 issue:10 pages:3372-3378 ispartof: location:United States status: published

Two new polymer systems, poly(3-phenylenevinylene)thiophene (P3PVT) and poly(3-phenyl)thiophene (P3PT), were designed with the aim of obtaining a helical conjugated polymer via a living polymerization. The polymerization proceeded without transfer and termination reactions via the Kumada catalyst transfer condensative polymerization (KCTCP) mechanism, confirming the living nature of the polymerization. Solvatochroism and circular dichroism (CD) experiments showed the helical nature of P3PVT and the stacking behavior of P3PT in poor solvent conditions. Block copolymers of 3-alkyl-substituted polythiophenes and helical P3PVT were prepared to determine the aggregation behavior of such systems. Solvatochroism, CD, and AFM measurements showed that the blocks influence each other’s behavior. If the P3AT block stacks before the helical P3PVT block organizes, one-handed helix formation is hindered. If helix formation occurs first, the stacking behavior is not influenced.

A network of self-assembled polystyrene beads was employed as a lithographic mask during covalent functionalization reactions on graphitic surfaces to create nanocorrals for confined molecular self-assembly studies. The beads were initially assembled into hexagonal arrays at the air-liquid interface and then transferred to the substrate surface. Subsequent electrochemical grafting reactions involving aryl diazonium molecules created covalently bound molecular units that were localized in the void space between the nanospheres. Removal of the bead template exposed hexagonally arranged circular nanocorrals separated by regions of chemisorbed molecules. Small molecule self-assembly was then investigated inside the resultant nanocorrals using scanning tunneling microscopy (STM) to highlight localized confinement effects. Overall, this work illustrates the utility of self-assembly principles to transcend length scale gaps in the development of hierarchically patterned molecular materials. ispartof: ACS Applied Materials and Interfaces vol:10 issue:14 pages:12005-12012 ispartof: location:United States status: published

Correlative imaging by fluorescence and force microscopy is an emerging technology to acquire orthogonal information at the nanoscale. Whereas atomic force microscopy excels at resolving the envelope structure of nanoscale specimens, fluorescence microscopy can detect specific molecular labels, which enables the unambiguous recognition of molecules in a complex assembly. Whereas correlative imaging at the micrometer scale has been established, it remains challenging to push the technology to the single-molecule level. Here, we used an integrated setup to systematically evaluate the factors that influence the quality of correlative fluorescence and force microscopy. Optimized data processing to ensure accurate drift correction and high localization precision results in image registration accuracies of ∼25 nm on organic fluorophores, which represents a 2-fold improvement over the state of the art in correlative fluorescence and force microscopy. Furthermore, we could extend the Atto532 fluorophore bleaching time ∼2-fold, by chemical modification of the supporting mica surface. In turn, this enables probing the composition of macromolecular complexes by stepwise photobleaching with high confidence. We demonstrate the performance of our method by resolving the stoichiometry of molecular subpopulations in a heterogeneous EcoRV-DNA nucleoprotein ensemble. ispartof: ACS Nano vol:12 issue:1 pages:168-177 ispartof: location:United States status: published

Tip-enhanced Raman scattering (TERS) microscopy is a unique analytical tool to provide complementary chemical and topographic information of surfaces with nanometric resolution. However, difficulties in reliably producing the necessary metallized scanning probe tips has limited its widespread utilisation, particularly in the case of cantilever-based atomic force microscopy. Attempts to alleviate tip related issues using colloidal or bottom-up engineered tips have so far not reported consistent probes for both Raman and topographic imaging. Here we demonstrate the reproducible fabrication of cantilever-based high-performance TERS probes for both topographic and Raman measurements, based on an approach that utilises noble metal nanowires as the active TERS probe. The tips show 10 times higher TERS contrasts than the most typically used electrochemically-etched tips, and show a reproducibility for TERS greater than 90%, far greater than found with standard methods. We show that TERS can be performed in tapping as well as contact AFM mode, with optical resolutions around or below 15 nm, and with a maximum resolution achieved in tapping-mode of 6 nm. Our work illustrates that superior TERS probes can be produced in a fast and cost-effective manner using simple wet-chemistry methods, leading to reliable and reproducible high-resolution and high-sensitivity TERS, and thus renders the technique applicable for a broad community. ispartof: Nanoscale vol:10 issue:16 pages:7556-7565 ispartof: location:England status: published