arXiv subjects

Klaus Müllen

Publications and source records attributed to Klaus Müllen.

32 records · Page 2Linked to original sources

arXiv2019

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 substrates. We show that this approach is well-suited to routinely monitor the geometry-dependent low-frequency modes of GNRs. In particular, we track the radial breathing-like mode (RBLM) and the shear-like mode (SLM) for 5-, 7- and 9-atom wide armchair GNRs (AGNRs) and compare their frequencies with first-principles calculations.

cond-mat.mtrl-sci↗

arXiv2019

Graphene Nanoribbons on Hexagonal Boron Nitride: Deposition and Transport Characterization

Chemically synthesized "cove"-type graphene nanoribbons (cGNRs) of different widths were brought into dispersion and drop-cast onto exfoliated hexagonal boron nitride (hBN) on a Si/SiO2 chip. With AFM we observed that the cGNRs form ordered domains aligned along the crystallographic axes of the hBN. Using electron beam lithography and metallization, we contacted the cGNRs with NiCr/Au, or Pd contacts and measured their I-V-characteristics. The transport through the ribbons was dominated by the Schottky behavior of the contacts between the metal and the ribbon.

cond-mat.mes-hall↗

arXiv2019

Structure-dependent electrical properties of graphene nanoribbon devices with graphene electrodes

Graphene nanoribbons (GNRs) are a novel and intriguing class of materials in the field of nanoelectronics, since their properties, solely defined by their width and edge type, are controllable with high precision directly from synthesis. Here we study the correlation between the GNR structure and the corresponding device electrical properties. We investigated a series of field effect devices consisting of a film of armchair GNRs with different structures (namely width and/or length) as the transistor channel, contacted with narrowly spaced graphene sheets as the source-drain electrodes. By analyzing several tens of junctions for each individual GNR type, we observe that the values of the output current display a width-dependent behavior, indicating electronic bandgaps in good agreement with the predicted theoretical values. These results provide insights into the link between the ribbon structure and the device properties, which are fundamental for the development of GNR-based electronics.

cond-mat.mes-hall↗

arXiv2019

Substrate transfer and ex situ characterization of on-surface synthesized graphene nanoribbons

Recent progress in the on-surface synthesis of graphene nanoribbons (GNRs) has given access to atomically precise narrow GNRs with tunable electronic band gaps that makes them excellent candidates for room-temperature switching devices such as field-effect transistors (FET). However, in spite of their exceptional properties, significant challenges remain for GNR processing and characterization. This contribution addresses some of the most important challenges, including GNR fabrication scalability, substrate transfer, long-term stability under ambient conditions and ex situ characterization. We focus on 7- and 9-atom wide armchair graphene nanoribbons (i.e, 7-AGNR; and 9-AGNR) grown on 200 nm Au(111)/mica substrates using a high throughput system. Transfer of both, 7- and 9-AGNRs from their Au growth sub-strate onto various target substrates for additional characterization is accomplished utilizing a polymer-free method that avoids residual contamination. This results in a homogeneous GNR film morphology with very few tears and wrinkles, as examined by atomic force microscopy. Raman spectroscopy indicates no significant degradation of GNR quality upon substrate transfer, and reveals that GNRs have remarkable stability under ambient conditions over a 24-month period. The transferred GNRs are analyzed using multi-wavelength Raman spectroscopy, which provides detailed insight into the wavelength dependence of the width-specific vibrational modes. Finally, we characterize the optical properties of 7- and 9-AGNRs via ultra-violet-visible (UV-Vis) spectroscopy

cond-mat.mtrl-sci↗

arXiv2018

Pump-Push-Probe for Ultrafast All-Optical Switching: The Case of a Nanographene Molecule

In the last two decades, the three-beams pump-push-probe (PPP) technique has become a well-established tool for investigating the multidimensional configurational space of a molecule, as it permits to disclose precious information about the multiple and often complex deactivation pathways of the excited molecule. From the spectroscopic point of view, such a tool has revealed details about the efficiency of charge pairs generation and conformational relaxation in p-conjugated molecules and macromolecules. In addition, PPP has been effectively utilised for modulating the gain signal in conjugated materials by taking advantage of the spectral overlap between stimulated emission and charge absorption in those systems. However, the relatively low stability of conjugated polymers under intense photoexcitation has been a crucial limitation for their real employment in plastic optical fibres (POFs) and for signal control applications. Here, we highlight the role of PPP for achieving ultrafast all-optical switching in p-conjugated systems. Furthermore, we report new experimental data on optical switching of a newly synthesised graphene molecule, namely dibenzo[hi,st]ovalene (DBOV). The superior environmental and photostability of DBOV and, in general, of graphene nanostructures can represent a great advantage for their effective applications in POFs and information and communications technology.

physics.chem-ph↗

arXiv2018

Charge transport mechanism in networks of armchair graphene nanoribbons

In graphene nanoribbons (GNRs), the lateral confinement of charge carriers opens a band gap, the key feature to enable novel graphene-based electronics. Successful synthesis of GNRs has triggered efforts to realize field-effect transistors (FETs) based on single ribbons. Despite great progress, reliable and reproducible fabrication of single-ribbon FETs is still a challenge that impedes applications and the understanding of the charge transport. Here, we present reproducible fabrication of armchair GNR-FETs based on a network of nanoribbons and analyze the charge transport mechanism using nine-atom wide and, in particular, five-atom-wide GNRs with unprecedented conductivity. We show formation of reliable Ohmic contacts and a yield of functional FETs close to unity by lamination of GNRs on the electrodes. Modeling the charge carrier transport in the networks reveals that this process is governed by inter-ribbon hopping mediated by nuclear tunneling, with a hopping length comparable to the physical length of the GNRs. Furthermore, we demonstrate that nuclear tunneling is a general charge transport characteristic of the GNR networks by using two different GNRs. Overcoming the challenge of low-yield single-ribbon transistors by the networks and identifying the corresponding charge transport mechanism puts GNR-based electronics in a new perspective.

cond-mat.mes-hall↗

arXiv2018

Engineering of robust topological quantum phases in graphene nanoribbons

Here we present a flexible strategy to realize robust nanomaterials exhibiting valence electronic structures whose fundamental physics is described by the SSH-Hamiltonian. These solid-state materials are realized using atomically precise graphene nanoribbons (GNR). We demonstrate the controlled periodic coupling of topological boundary states at junctions of armchair GNRs of different widths to create quasi-1D trivial and non-trivial electronic quantum phases. Their topological class is experimentally determined by drawing upon the bulk-boundary correspondence and measuring the presence (non-trivial) or absence (trivial) of localized end states by scanning tunneling spectroscopy (STS). The strategy we propose has the potential to tune the band width of the topological electronic bands close to the energy scale of proximity induced spin-orbit coupling or superconductivity, and may allow the realization of Kitaev like Hamiltonians and Majorana type end states.

cond-mat.mes-hall↗

arXiv2017

Strong Exciton-Photon Coupling in a Nanographene Filled Microcavity

Dibenzo[\emph{hi,st}]ovalene (DBOV) - a quasi-zero-dimensional `nanographene' - displays strong, narrow, and well-defined optical-absorption transitions at room temperature. On placing a DBOV-doped polymer film into an optical microcavity, we demonstrate strong coupling of the \textbf{0 $\rightarrow$ 0'} electronic and \textbf{0 $\rightarrow$ 1'} vibrational transitions to a confined cavity mode, with coupling energies of 104 meV and 40 meV, respectively. Photoluminescence measurements indicate that the polariton population is distributed between the lower and middle polariton branches at energies approximately coincident with the emission of the DBOV, indicating polariton population via an optical pumping mechanism.

physics.optics↗

arXiv2017

Short-Channel Field Effect Transistors with 9-Atom and 13-Atom wide Graphene Nanoribbons

Bottom-up synthesized GNRs and GNR heterostructures have promising electronic properties for high performance field effect transistors (FETs) and ultra-low power devices such as tunnelling FETs. However, the short length and wide band gap of these GNRs have prevented the fabrication of devices with the desired performance and switching behaviour. Here, by fabricating short channel (Lch ~20 nm) devices with a thin, high-k gate dielectric and a 9-atom wide (0.95 nm) armchair GNR as the channel material, we demonstrate FETs with high on-current (Ion >1 uA at Vd = -1 V) and high Ion/Ioff ~10^5 at room temperature. We find that the performance of these devices is limited by tunnelling through the Schottky barrier (SB) at the contacts and we observe an increase in the transparency of the barrier by increasing the gate field near the contacts. Our results thus demonstrate successful fabrication of high performance short-channel FETs with bottom-up synthesized armchair GNRs.

cond-mat.mes-hall↗

arXiv2016

Raman fingerprints of atomically precise graphene nanoribbons

Bottom-up approaches allow the production of ultra-narrow and atomically precise graphene nanoribbons (GNRs), with electronic and optical properties controlled by the specific atomic structure. Combining Raman spectroscopy and ab-initio simulations, we show that GNR width, edge geometry and functional groups all influence their Raman spectra. The low-energy spectral region below 1000 cm-1 is particularly sensitive to edge morphology and functionalization, while the D peak dispersion can be used to uniquely fingerprint the presence of GNRs, and differentiates them from other sp2 carbon nanostructures.

cond-mat.mes-hall↗

arXiv2014

Electronic Band Dispersion of Graphene Nanoribbons via Fourier-Transformed Scanning Tunneling Spectroscopy

Atomically precise armchair graphene nanoribbons of width $N=7$ (7-AGNRs) are investigated by scanning tunneling spectroscopy (STS) on Au(111). The analysis of energy-dependent standing wave patterns of finite length ribbons allows, by Fourier transformation, the direct extraction of the dispersion relation of frontier electronic states. Aided by density functional theory calculations, we assign the states to the valence band, the conduction band and the next empty band of 7-AGNRs, determine effective masses of $0.42\pm 0.08\,m_e$, $0.40\pm 0.18\,m_e$ and $0.20\pm 0.03\,m_e$, respectively, and a band gap of $2.37\pm 0.06$ eV.

cond-mat.mes-hall↗

arXiv2014

Comparing charge transfer tuning effects by chemical substitution and uniaxial pressure in the organic charge transfer complex tetramethoxypyrene-tetracyanoquinodimethane

In the search for novel organic charge transfer salts with variable charge transfer degree we study the effects of two modifications to the recently synthesized donor-acceptor Tetramethoxypyrene (TMP)-Tetracyanoquinodimethane (TCNQ). One is of chemical nature by substituting the acceptor TCNQ molecules by F4TCNQ molecules. The second consists in simulating the application of uniaxial pressure along the stacking axis of the system. In order to test the chemical substitution, we have grown single crystals of TMP-F4TCNQ and analyzed its electronic structure via electronic transport measurements, ab initio density functional theory (DFT) calculations and UV/VIS/IR absorption spectroscopy. This system shows an almost ideal geometrical overlap of nearly planar molecules alternately stacked (mixed stack) and this arrangement is echoed by a semiconductor-like transport behavior with an increased conductivity along the stacking direction. This is in contrast to TMP-TCNQ which shows a less pronounced anisotropy and a smaller conductivity response. Our bandstructure calculations confirm the one-dimensional behavior of TMP-F4TCNQ with pro- nounced dispersion only along the stacking axis. Infrared measurements illustrating the CN vibration frequency shift in F4TCNQ suggest however no improvement on the degree of charge transfer in TMP-F4TCNQ with respect to TMP-TCNQ. In both complexes about 0.1 is transferred from TMP to the acceptor. Concerning the pressure effect, our DFT calculations on designed TMP-TCNQ and TMP-F4TCNQ structures under different pressure conditions show that application of uniaxial pressure along the stacking axis of TMP-TCNQ may be the route to follow in order to obtain a much more pronounced charge transfer.

cond-mat.mtrl-sci↗

arXiv2013

The abundances of hydrocarbon functional groups in the interstellar medium inferred from laboratory spectra of hydrogenated and methylated polycyclic aromatic hydrocarbons

Infrared (IR) absorption spectra of individual polycyclic aromatic hydrocarbons (PAHs) containing methyl (-CH3), methylene (>CH2), or diamond-like *CH groups and IR spectra of mixtures of methylated and hydrogenated PAHs prepared by gas phase condensation were measured at room temperature (as grains in pellets) and at low temperature (isolated in Ne matrices). In addition, the PAH blends were subjected to an in-depth molecular structure analysis by means of high-performance liquid chromatography, nuclear magnetic resonance spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Supported by calculations at the density functional theory level, the laboratory results were applied to analyze in detail the aliphatic absorption complex of the diffuse interstellar medium at 3.4 mu-m and to determine the abundances of hydrocarbon functional groups. Assuming that the PAHs are mainly locked in grains, aliphatic CHx groups (x = 1,2,3) would contribute approximately in equal quantities to the 3.4 mu-m feature (N_{CHx} / N_{H} approx 10^{-5} - 2 * 10^{-5}). The abundances, however, may be two to four times lower if a major contribution to the 3.4 mu-m feature comes from molecules in the gas phase. Aromatic =CH groups seem to be almost absent from some lines of sight, but can be nearly as abundant as each of the aliphatic components in other directions (N_{=CH} / N_{H} < 2 * 10^{-5}; upper value for grains). Due to comparatively low binding energies, astronomical IR emission sources do not display such heavy excess hydrogenation. At best, especially in proto-planetary nebulae, >CH2 groups bound to aromatic molecules, i.e., excess hydrogens on the molecular periphery only, can survive the presence of a nearby star.

astro-ph.GA↗

arXiv2013

Turbostratic graphitic microstructures: electronically decoupled multilayer graphene devices with robust high charge carrier mobility

Carbon nanomaterials continue to amaze scientists due to their exceptional physical properties. Recently there have been theoretical predictions and first reports on graphene multilayers, where, due to the rotation of the stacked layers, outstanding electronic properties are retained while the susceptibility to degradation and mechanical stress is strongly reduced due to the multilayer nature. Here we show that fully turbostratic multilayer graphitic microstructures combine the high charge carrier mobilities necessary for advanced electronic and spintronic devices with the robustness of graphitic structures. Structural characterization of disk-shaped graphitic microstructures using Raman spectroscopy and Transmission Electron Microscopy (TEM) reveals Moiré and diffraction patterns corroborating their turbostratic nature. Electronic transport characterization yields reproducible high mobilities > 105 cm^2(Vs)^(-1) independent of the disks thickness, which is a direct consequence of the electronic decoupling induced by the turbostratic stacking.

cond-mat.mtrl-sci↗