0000000001309193
AUTHOR
Roman Fasel
A Universal Length-Dependent Vibrational Mode in Graphene Nanoribbons
Graphene nanoribbons (GNRs) have attracted considerable interest as their atomically tunable structure makes them promising candidates for future electronic devices. However, obtaining detailed information about the length of GNRs has been challenging and typically relies on low-temperature scanning tunneling microscopy. Such methods are ill-suited for practical device application and characterization. In contrast, Raman spectroscopy is a sensitive method for the characterization of GNRs, in particular for investigating their width and structure. Here, we report on a length-dependent, Raman active low-energy vibrational mode that is present in atomically precise, bottom-up synthesized armch…
On-Surface Synthesis of Unsaturated Carbon Nanostructures with Regularly Fused Pentagon–Heptagon Pairs
Multiple fused pentagon-heptagon pairs are frequently found as defects at the grain boundaries of the hexagonal graphene lattice and are suggested to have a fundamental influence on graphene-related materials. However, the construction of sp2-carbon skeletons with multiple regularly fused pentagon-heptagon pairs is challenging. In this work, we found that the pentagon-heptagon skeleton of azulene was rearranged during the thermal reaction of an azulene-incorporated organometallic polymer on Au(111). The resulting sp2-carbon frameworks were characterized by high-resolution scanning probe microscopy techniques and feature novel polycyclic architectures composed of multiple regularly fused pen…
Chemical Vapor Deposition Synthesis and Terahertz Photoconductivity of Low-Band-Gap N = 9 Armchair Graphene Nanoribbons.
Recent advances in bottom-up synthesis of atomically defined graphene nanoribbons (GNRs) with various microstructures and properties have demonstrated their promise in electronic and optoelectronic devices. Here we synthesized N = 9 armchair graphene nanoribbons (9-AGNRs) with a low optical band gap of ∼1.0 eV and extended absorption into the infrared range by an efficient chemical vapor deposition process. Time-resolved terahertz spectroscopy was employed to characterize the photoconductivity in 9-AGNRs and revealed their high intrinsic charge-carrier mobility of approximately 350 cm2·V-1·s-1.
Large-Cavity Coronoids with Different Inner and Outer Edge Structures
Coronoids, polycyclic aromatic hydrocarbons with geometrically defined cavities, are promising model structures of porous graphene. Here, we report the on-surface synthesis of C168 and C140 coronoids, referred to as [6]- and [5]coronoid, respectively, using 5,9-dibromo-14-phenylbenzo[m]tetraphene as the precursor. These coronoids entail large cavities (>1 nm) with inner zigzag edges, distinct from their outer armchair edges. While [6]coronoid is planar, [5]coronoid is not. Low-temperature scanning tunneling microscopy/spectroscopy and noncontact atomic force microscopy unveil structural and electronic properties in accordance with those obtained from density functional theory calculation…
Optimized substrates and measurement approaches for Raman spectroscopy of graphene nanoribbons
The on-surface synthesis of graphene nanoribbons (GNRs) allows for the fabrication of atomically precise narrow GNRs. Despite their exceptional properties which can be tuned by ribbon width and edge structure, significant challenges remain for GNR processing and characterization. In this contribution, we use Raman spectroscopy to characterize different types of GNRs on their growth substrate and to track their quality upon substrate transfer. We present a Raman-optimized (RO) device substrate and an optimized mapping approach that allows for acquisition of high-resolution Raman spectra, achieving enhancement factors as high as 120 with respect to signals measured on standard SiO2/Si substra…
On-Surface Synthesis of Antiaromatic and Open-Shell Indeno[2,1- b ]fluorene Polymers and Their Lateral Fusion into Porous Ribbons
Polycyclic hydrocarbons have received great attention due to their potential role in organic electronics and, for open-shell systems with unpaired electron densities, in spintronics and da-ta storage. However, the intrinsic instability of polyradical hydrocarbons severely limits de-tailed investigations of their electronic structure. Here, we report the on-surface synthesis of conjugated polymers consisting of indeno[2,1-b]fluorene units, which are antiaromatic and open-shell biradicaloids. The observed reaction products, which also include a non-benzenoid porous ribbon arising from lateral fusion of unprotected indeno[2,1-b]fluorene chains, have been characterized via low temperature scann…
On-surface Synthesis of a Chiral Graphene Nanoribbon with Mixed Edge Structure.
Abstract Chiral graphene nanoribbons represent an important class of graphene nanomaterials with varying combinations of armchair and zigzag edges conferring them unique structure‐dependent electronic properties. Here, we describe the on‐surface synthesis of an unprecedented cove‐edge chiral GNR with a benzo‐fused backbone on a Au(111) surface using 2,6‐dibromo‐1,5‐diphenylnaphthalene as precursor. The initial precursor self‐assembly and the formation of the chiral GNRs upon annealing are revealed, along with a relatively small electronic bandgap of approximately 1.6 eV, by scanning tunnelling microscopy and spectroscopy.
Overcoming Steric Hindrance in Aryl‐Aryl Homocoupling via On‐Surface Copolymerization
On-surface synthesis is a unique tool for growing low-dimensional carbon nanomaterials with precise structural control down to the atomic level. This novel approach relies on carefully designed precursor molecules, which are deposited on suitable substrates and activated to ultimately form the desired nanostructures. One of the most applied reactions to covalently interlink molecular precursors is dehalogenative aryl-aryl coupling. Despite the versatility of this approach, many unsuccessful attempts are also known, most of them associated to the poor capability of the activated precursors to couple to each other. Such failure is often related to the steric hindrance between reactants, which…
On-Surface Synthesis of Dibenzohexacenohexacene and Dibenzopentaphenoheptaphene
We report the on-surface synthesis and gas-phase theoretical studies of two novel nanographenes, namely, dibenzohexacenohexacene and dibenzopentaphenoheptaphene, using 8,8′-dibromo-5,5′-bibenzo[rst]pentaphene as a precursor. These nanographenes display a combination of armchair and zigzag edges, as shown by noncontact atomic force microscopy (nc-AFM), and their electronic properties are elucidated by density functional theory (DFT) calculations which reveal relatively low HOMO-LUMO energy gaps of about 1.75 eV.
On-Surface Synthesis of Oligo(indenoindene)
Fully conjugated ladder polymers (CLP) possess unique optical and electronic properties, and are considered promis-ing materials for applications in (opto)electronic devices. Poly(indenoindene) is a CLP consisting of an alternating array of five- and six-membered rings, which has remained elusive so far. Here, we report an on-surface synthesis of oligo(indenoindene) on Au(111). Its structure and a low elec-tronic bandgap have been elucidated by low-temperature scanning tunneling microscopy and spectroscopy and non-contact atomic force microscopy, complemented by density functional theory calculations. Achieving defect-free seg-ments of oligo(indenoindene) offers an exclusive insight into th…
Optical Imaging and Spectroscopy of Atomically Precise Armchair Graphene Nanoribbons
We report the optical imaging and absorption spectroscopy on atomically precise armchair graphene nanoribbons (GNRs) on insulating fused silica substrates. This is achieved by controlling light polarization on macroscopically aligned GNRs which greatly enhances the optical contrast of the submonolayer GNRs on the insulating substrates. We measure the linear absorption spectra of 7-armchair and 9-armchair GNRs in this study, and the experimental data agree qualitatively with ab inito calculation results. The polarization spectroscopy technique enables an unambiguous optical identification of GNRs and provides a rapid tool to characterize the transferred film over a large area.
CCDC 2021698: Experimental Crystal Structure Determination
Related Article: Ashok Keerthi, Carlos Sánchez‐Sánchez, Okan Deniz, Pascal Ruffieux, Dieter Schollmeyer, Xinliang Feng, Akimitsu Narita, Roman Fasel, Klaus Müllen|2020|Chem.Asian J.|15|3807|doi:10.1002/asia.202001008
CCDC 1980964: Experimental Crystal Structure Determination
Related Article: Marco Di Giovannantonio, Qiang Chen, José I. Urgel, Pascal Ruffieux, Carlo A. Pignedoli, Akimitsu Narita, Klaus Müllen, Roman Fasel|2020|J.Am.Chem.Soc.|142|12925|doi:10.1021/jacs.0c05701
CCDC 1903872: Experimental Crystal Structure Determination
Related Article: Marco Di Giovannantonio, Kristjan Eimre, Aliaksandr V. Yakutovich, Qiang Chen, Shantanu Mishra, José I. Urgel, Carlo A. Pignedoli, Pascal Ruffieux, Klaus Müllen, Akimitsu Narita, Roman Fasel|2019|J.Am.Chem.Soc.|141|12346|doi:10.1021/jacs.9b05335