In the last decade, ionic liquids have shown great promise in a plethora of applications. However, little attention has been paid to the characterisation of the purity of these fluids, which has ultimately led to non-reproducible data in the literature. In order to facilitate specification of ionic liquids, a number of analytical protocols with their limits of detection (where available) have been compiled, including methods of other authors. In particular, quantitative methods have been developed and summarised for the determination of the total ionic liquid content, residual unreacted ionic liquid starting material and by-products (amines, alkylating agents, inorganic halides), solvents from extraction procedures and water, in addition to decomposition products and total volatiles.
Graphene nanoribbons (GNRs) have attracted a strong interest from researchers worldwide, as they constitute an emerging class of quantum-designed materials. The major challenges towards their exploitation in electronic applications include reliable contacting, complicated by their small size (< 50 nm), as well as the preservation of their physical properties upon device integration.In this combined experimental and theoretical study, we report on the quantum dot (QD) behavior of atomically precise GNRs integrated in a device geometry. The devices consist of a film of aligned 5-atoms wide GNRs (5-AGNRs) transferred onto graphene electrodes with a sub 5-nm nanogap. We demonstrate that the narrow-bandgap 5-AGNRs exhibit metal-like behavior resulting in linear IV curves for low bias voltages at room temperature and single-electron transistor behavior for temperatures below 150 K. By performing spectroscopy of the molecular levels at 13 K, we obtain addition energies in the range of 200-300 meV. DFT calculations predict comparable addition energies and reveal the presence of two electronic states within the bandgap of infinite ribbons when the finite length of the 5-AGNRs is accounted for. By demonstrating the preservation of the 5-AGNRs electronic properties upon device integration, as demonstrated by transport spectroscopy, our study provides a critical step forward in the realisation of more exotic GNR-based nano-electronic devices.
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. Herein, Raman spectroscopy is used to characterize different types of GNRs on their growth substrate and track their quality upon substrate transfer. A Raman‐optimized (RO) device substrate and an optimized mapping approach are presented that allow for the acquisition of high‐resolution Raman spectra, achieving enhancement factors as high as 120 with respect to signals measured on standard SiO2/Si substrates. This approach is well suited to routinely monitor the geometry‐dependent low‐frequency modes of GNRs. In particular, the radial breathing‐like mode (RBLM) and the shear‐like mode (SLM) for 5‐, 7‐, and 9‐atom‐wide armchair GNRs (AGNRs) are tracked and their frequencies are compared with first‐principles calculations.
Graphene nanoribbons (GNRs) have attracted much interest due to their largely modifiable electronic properties. Manifestation of these properties requires atomically precise GNRs which can be achieved through a bottom–up synthesis approach. This has recently been applied to the synthesis of width‐modulated GNRs hosting topological electronic quantum phases, with valence electronic properties that are well captured by the Su–Schrieffer–Heeger (SSH) model describing a 1D chain of interacting dimers. Here, ultralow bandgap GNRs with charge carriers behaving as massive Dirac fermions can be realized when their valence electrons represent an SSH chain close to the topological phase boundary, i.e., when the intra‐ and interdimer coupling become approximately equal. Such a system has been achieved via on‐surface synthesis based on readily available pyrene‐based precursors and the resulting GNRs are characterized by scanning probe methods. The pyrene‐based GNRs (pGNRs) can be processed under ambient conditions and incorporated as the active material in a field effect transistor. A quasi‐metallic transport behavior is observed at room temperature, whereas at low temperature, the pGNRs behave as quantum dots showing single‐electron tunneling and Coulomb blockade. This study may enable the realization of devices based on carbon nanomaterials with exotic quantum properties.
Single molecule pulling experiments provide information about interactions in biomolecules that cannot be obtained by any other method. However, the reconstruction of the molecule's free energy profile from the experimental data is still a challenge, in particular for the unstable barrier regions. We propose a new method for obtaining the full profile by introducing a periodic ramp and using Jarzynski's identity for obtaining equilibrium quantities from non-equilibrium data. Our simulated experiments show that this method delivers significant more accurate data than previous methods, under the constraint of equal experimental effort.
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 lengthdependent, Raman active low-energy vibrational mode that is present in atomically precise, bottom-up synthesized armchair graphene nanoribbons (AGNRs). Our Raman study demonstrates that this mode is present in all families of AGNRs and provides information on their length. Our spectroscopic findings are corroborated by scanning tunneling microscopy images and supported by first-principles calculations that allow us to attribute this mode to a longitudinal acoustic phonon. Finally, we show that this mode is a sensitive probe for the overall structural integrity of the ribbons and their interaction with technologically relevant substrates.
One of the main challenges to upscale the fabrication of molecular devices is to achieve a mechanically stable device with reproducible and controllable electronic features, operating at room temperature 1,2. This is crucial because structural and electronic fluctuations can lead to significant changes in the transport characteristics at the electrode-molecule interface 3,4. In this study, we report on the realization of a mechanically and electronically robust graphene-based molecular junction. Robustness is achieved by separating the requirements for mechanical and electronic stability at the molecular level. Mechanical stability is obtained by anchoring molecules directly to the substrate, rather than to graphene electrodes, using a silanization reaction. Electronic stability is achieved by adjusting the π-π orbitals overlap of the conjugated head groups between neighbouring molecules. The molecular devices exhibit stable current-voltage (I-V) characteristics up to bias voltages of 2.0 V with reproducible transport features in the temperature range from 20 K to 300 K. To realize reliable graphene-based junctions, several issues exist to date and need to be addressed. First, graphene-based junctions have been reported to exhibit signatures similar to those of molecules, with gate-dependent resonance features, such as Coulomb blockade 5,6 , quantum interference 7 and Fabry-Perrot resonances 8. Second, connecting molecules to the graphene remains challenging due to the lack of control on the electrode geometry at the nanoscale 4,5,8-10. Achieving both mechanical stability and electrical reproducibility at the same time impose different requirements on the junction properties 3,11. Finding the proper balance between electronic and mechanical stability is therefore challenging. Weakly coupled π − π stacking is believed to be an appealing strategy to anchor molecules to the contact electrodes 3 , offering advantages such as high thermoelectric efficiency. However, this approach has been shown to lead to mechanically unstable junctions 12. Alternatively, molecules have also been bonded covalently to graphene, yielding mechanically stable junctions 10. However, transport through strongly coupled molecules is expected to be heavily influenced by the electrode geometry, edge termination and crystallographic structure, leading to a large variability in the shape of the current-voltage characteristics 3. Third, junction-to-junctions via molecular orbital gating. Nature nanotechnology 1 (2018).
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