Thiol Carbazole Self-Assembled Monolayers as Tunable Carrier Injecting Interlayers for Organic Transistors and Complementary Circuits.

The significant contact resistance at the metal-semiconductor interface is a well-documented issue for organic thin-film transistors (OTFTs) that hinders device and circuit performance. Here, this issue is tackled by developing three new thiol carbazole-based self-assembled monolayer (SAM) molecules, namely tBu-2SCz, 2SCz, and Br-2SCz, and utilizing them as carrier-selective injection interlayers. The SAMs alter the work function of gold electrodes by more than 1 eV, making them suitable for use in hole and electron-transporting OTFTs.

Imaging Dihydrogen Bond-Driven Assembly of Borazine on Au(111).

Dihydrogen bonding (DHB) is a peculiar type of attractive interaction occurring between a partially positively charged hydrogen atom and a partially negatively charged hydrogen atom. Borazine represents a prototypical molecule exhibiting dihydrogen bonding in both gas phase, as well as in its crystalline form. For borazine assemblies on solid surfaces, a direct observation and characterization of dihydrogen bonding has remained elusive, possibly due to an intricate interplay of substrate-molecule and intermolecular interactions.

Real-space investigation of polarons in hematite FeO.

In polarizable materials, electronic charge carriers interact with the surrounding ions, leading to quasiparticle behavior. The resulting polarons play a central role in many materials properties including electrical transport, interaction with light, surface reactivity, and magnetoresistance, and polarons are typically investigated indirectly through these macroscopic characteristics. Here, noncontact atomic force microscopy (nc-AFM) is used to directly image polarons in FeO at the single quasiparticle limit.

Emergence of Band Structure in a Two-Dimensional Metal-Organic Framework upon Hierarchical Self-Assembly.

Two-dimensional metal-organic frameworks (2D-MOFs) represent a category of atomically thin materials that combine the structural tunability of molecular systems with the crystalline structure characteristic of solids. The strong bonding between the organic linkers and transition metal centers is expected to result in delocalized electronic states. However, it remains largely unknown how the band structure in 2D-MOFs emerges through the coupling of electronic states in the building blocks.

Probing dynamic covalent chemistry in a 2D boroxine framework by near-ambient pressure X-ray photoelectron spectroscopy.

Dynamic covalent chemistry is a powerful approach to design covalent organic frameworks, where high crystallinity is achieved through reversible bond formation. Here, we exploit near-ambient pressure X-ray photoelectron spectroscopy to elucidate the reversible formation of a two-dimensional boroxine framework. By mapping the pressure-temperature parameter space, we identify the regions where the rates of the condensation and hydrolysis reactions become dominant, being the key to enable the thermodynamically controlled growth of crystalline frameworks.

In Situ Observation of C-C Coupling and Step Poisoning During the Growth of Hydrocarbon Chains on Ni(111).

The synthesis of high-value fuels and plastics starting from small hydrocarbon molecules plays a central role in the current transition towards renewable energy. However, the detailed mechanisms driving the growth of hydrocarbon chains remain to a large extent unknown. Here we investigated the formation of hydrocarbon chains resulting from acetylene polymerization on a Ni(111) model catalyst surface.

Exploiting Cooperative Catalysis for the On-Surface Synthesis of Linear Heteroaromatic Polymers via Selective C-H Activation.

Regiospecific C-H activation is a promising approach to achieve extended polymers with tailored structures. While a recent on-surface synthetic approach has enabled regioselective homocoupling of heteroaromatic molecules, only small oligomers have been achieved. Herein, selective C-H activation for dehydrogenative C-C couplings of hexaazatriphenylene by Scholl reaction is reported for the first time.

Imaging Charge Localization in a Conjugated Oligophenylene.

Polaron formation in conjugated polymers has a major impact on their optical and electronic properties. In polyphenylene, the molecular conformation is determined by a delicate interplay between electron delocalization and steric effects. Injection of excess charges is expected to increase the degree of conjugation, leading to structural distortions of the chain.

Manipulating and Probing the Distribution of Excess Electrons in an Electrically Isolated Self-Assembled Molecular Structure.

Exploiting single electrical charges and their mutual interactions for computation has been proposed as a concept for future nanoelectronics. Controlling and probing charge transfer in electrically isolated atomic-scale structures are fundamental to push its experimental realization. Here, we controllably inject individual excess electrons and study their distribution in a self-assembled structure supported on a nonconductive substrate.

Charge-Induced Structural Changes in a Single Molecule Investigated by Atomic Force Microscopy.

Intramolecular structural relaxations occurring upon electron transfer are crucial in determining the rate of redox reactions. Here, we demonstrate that subangstrom structural changes occurring upon single-electron charging can be quantified by means of atomically resolved atomic force microscopy (AFM) for the case of single copper(II)phthalocyanine (CuPc) molecules deposited on an ultrathin NaCl film. Imaging the molecule in distinct charge states (neutral and anionic) reveals characteristic differences in the AFM contrast.

Accessing a Charged Intermediate State Involved in the Excitation of Single Molecules.

Intermediate states are elusive to many experimental techniques due to their short lifetimes. Here, by performing single-electron alternate charging scanning tunneling microscopy of molecules on insulators, we accessed a charged intermediate state involved in the rapid toggling of individual metal phthalocyanines deposited on NaCl films. By stabilizing the transient species, we reveal how electron injection into the lowest unoccupied molecular orbital leads to a pronounced change in the adsorption geometry, characterized by a different azimuthal orientation.

The new FAST module: A portable and transparent add-on module for time-resolved investigations with commercial scanning probe microscopes.

Time resolution is one of the most severe limitations of scanning probe microscopies (SPMs), since the typical image acquisition times are in the order of several seconds or even few minutes. As a consequence, the characterization of dynamical processes occurring at surfaces (e.g.

Resolving the Unpaired-Electron Orbital Distribution in a Stable Organic Radical by Kondo Resonance Mapping.

The adsorption geometry and the electronic structure of a Blatter radical derivative on a gold surface were investigated by a combination of high-resolution noncontact atomic force microscopy and scanning tunneling microscopy. While the hybridization with the substrate hinders direct access to the molecular states, we show that the unpaired-electron orbital can be probed with Ångström resolution by mapping the spatial distribution of the Kondo resonance. The Blatter derivative features a peculiar delocalization of the unpaired-electron orbital over some but not all moieties of the molecule, such that the Kondo signature can be related to the spatial fingerprint of the orbital.

Doping of epitaxial graphene by direct incorporation of nickel adatoms.

Direct incorporation of Ni adatoms during graphene growth on Ni(111) is evidenced by scanning tunneling microscopy. The structure and energetics of the observed defects is thoroughly characterized at the atomic level on the basis of density functional theory calculations. Our results show the feasibility of a simple scalable method, which could be potentially used for the realization of macroscopic practical devices, to dope graphene with a transition metal.

The Environment-Dependent Behavior of the Blatter Radical at the Metal-Molecule Interface.

Stable organic radicals have potential applications for building organic spintronic devices. To fulfill this potential, the interface between organic radicals and metal electrodes must be well characterized. Here, through a combined effort that includes synthesis, scanning tunneling microscopy, X-ray spectroscopy, and single-molecule conductance measurements, we comprehensively probe the electronic interaction between gold metal electrodes and a benchtop stable radical-the Blatter radical.

Mapping orbital changes upon electron transfer with tunnelling microscopy on insulators.

Electron transfer plays a crucial part in many chemical reactions, including photosynthesis, combustion and corrosion. But even though redox-state transitions change the electronic structure of the molecules involved, mapping these changes at the single-molecule level is challenging. Scanning tunnelling microscopy provides insights into the orbital structure of single molecules and their interactions, but requires the use of a conductive substrate that keeps molecules in a given charge state and thereby suppresses redox-state transitions.

Tuning ultrafast electron injection dynamics at organic-graphene/metal interfaces.

We compare the ultrafast charge transfer dynamics of molecules on epitaxial graphene and bilayer graphene grown on Ni(111) interfaces through first principles calculations and X-ray resonant photoemission spectroscopy. We use 4,4'-bipyridine as a prototypical molecule for these explorations as the energy level alignment of core-excited molecular orbitals allows ultrafast injection of electrons from a substrate to a molecule on a femtosecond timescale. We show that the ultrafast injection of electrons from the substrate to the molecule is ∼4 times slower on weakly coupled bilayer graphene than on epitaxial graphene.

Real-time imaging of adatom-promoted graphene growth on nickel.

Single adatoms are expected to participate in many processes occurring at solid surfaces, such as the growth of graphene on metals. We demonstrate, both experimentally and theoretically, the catalytic role played by single metal adatoms during the technologically relevant process of graphene growth on nickel (Ni). The catalytic action of individual Ni atoms at the edges of a growing graphene flake was directly captured by scanning tunneling microscopy imaging at the millisecond time scale, while force field molecular dynamics and density functional theory calculations rationalize the experimental observations.

Imaging on-surface hierarchical assembly of chiral supramolecular networks.

The bottom-up assembly of chiral structures usually relies on a cascade of molecular recognition interactions. A thorough description of these complex stereochemical mechanisms requires the capability of imaging multilevel coordination in real-time. Here we report the first direct observation of hierarchical expression of supramolecular chirality at work, for 10,10'-dibromo-9,9'-bianthryl (DBBA) on Cu(111).

Crystallization of a Two-Dimensional Hydrogen-Bonded Molecular Assembly: Evolution of the Local Structure Resolved by Atomic Force Microscopy.

Structures of the aromatic N-heterocyclic hexaazatriphenylene (HAT) molecular synthon obtained by surface-assisted self-assembly were analyzed with sub-Å resolution by means of noncontact atomic force microscopy (nc-AFM), both in the kinetically trapped amorphous state and in the thermodynamically stable crystalline phase. These results reveal how the crystallization governs the length scale of the network order for non-flexible molecular species without affecting the local bonding schemes. The capability of nc-AFM to accurately resolve structural relaxations will be highly relevant for the characterization of vitreous two-dimensional supramolecular materials.

Activation of Cu(111) surface by decomposition into nanoclusters driven by CO adsorption.

The (111) surface of copper (Cu), its most compact and lowest energy surface, became unstable when exposed to carbon monoxide (CO) gas. Scanning tunneling microscopy revealed that at room temperature in the pressure range 0.1 to 100 Torr, the surface decomposed into clusters decorated by CO molecules attached to edge atoms.

Switchable graphene-substrate coupling through formation/dissolution of an intercalated Ni-carbide layer.

Control over the film-substrate interaction is key to the exploitation of graphene's unique electronic properties. Typically, a buffer layer is irreversibly intercalated "from above" to ensure decoupling. For graphene/Ni(111) we instead tune the film interaction "from below".

Nanobubbles at GPa Pressure under Graphene.

We provide direct evidence that irradiation of a graphene membrane on Ir with low-energy Ar ions induces formation of solid noble-gas nanobubbles. Their size can be controlled by thermal treatment, reaching tens of nanometers laterally and height of 1.5 nm upon annealing at 1080 °C.

Temperature-driven changes of the graphene edge structure on Ni(111): substrate vs hydrogen passivation.

Atomic-scale description of the structure of graphene edges on Ni(111), both during and post growth, is obtained by scanning tunneling microscopy (STM) in combination with density functional theory (DFT). During growth, at 470 °C, fast STM images (250 ms/image) evidence graphene flakes anchored to the substrate, with the edges exhibiting zigzag or Klein structure depending on the orientation. If growth is frozen, the flake edges hydrogenate and detach from the substrate, with hydrogen reconstructing the Klein edges.

Atomic Scale Identification of Coexisting Graphene Structures on Ni(111).

Through a combined scanning tunneling microscopy (STM) and density functional theory (DFT) approach, we provide a full characterization of the different chemisorbed configurations of epitaxial graphene coexisting on the Ni(111) single crystal surface. Top-fcc, top-hcp, and top-bridge are found to be stable structures with comparable adsorption energy. By comparison of experiments and simulations, we solve an existing debate, unambiguously distinguishing these configurations in high-resolution STM images and characterizing the transitions between adjacent domains.