arXiv subjects

Klaus Müllen

Publications and source records attributed to Klaus Müllen.

At least 19 recordsLinked to original sources

arXiv2026

One-dimensional carbon nanostructures with periodic graphitic nitrogen substitution

Heteroatom substitution is a powerful route to tune the chemical and electronic properties of carbon nanomaterials. In particular, replacement of an sp2 hybridized carbon atom in the graphene lattice with a nitrogen atom (denoted as graphitic nitrogen) induces substantial changes in the electronic properties. These include changes in the band structure that can influence electronic transport, and magnetism. A key requirement for applications is both the periodic and precise incorporation of the heteroatoms in extended carbon lattices. Here, we report the on-surface synthesis and characterization of two one dimensional carbon nanostructures, a polymer and a graphene nanoribbon, consisting of periodically incorporated graphitic nitrogen atoms. The on-surface reactions toward formation of the nanostructures were monitored by scanning tunneling microscopy. The bond-resolved chemical structures of the reaction intermediates and products were investigated by atomic force microscopy, which enabled atomic-scale visualization of the graphitic nitrogen sites. The electronic properties of the nanostructures were studied by scanning tunneling spectroscopy and density functional theory calculations. Our analyses revealed the presence of localized nitrogen-centered electronic states. In the gas phase where the nanostructures are in a neutral charge state, these states undergo spin polarization leading to an open-shell ground state. Upon adsorption on Au(111), the nanostructures exhibit electron transfer to the surface, which resulted in a closed-shell ground state. Our results demonstrate a straightforward and generally applicable route to synthesize graphitic nitrogen-substituted carbon nanomaterials with potential applications in spintronics, catalysis and energy storage.

cond-mat.mes-hall↗

arXiv2026

Step-Edge Passivation and Quantitative Raman Mapping of Transfer Quality in Aligned Graphene Nanoribbons

The transfer of aligned graphene nanoribbons from metallic growth surfaces to device-compatible platforms remains a central bottleneck for nanoribbon electronics. Here, we investigate step-edge passivation of vicinal Au(788) by chevron-GNRs as a strategy to improve the transfer of aligned 9-armchair graphene nanoribbons. Scanning tunneling microscopy reveals that chevron-GNRs preferentially occupy step-edges, effectively acting as passivators that displace 9-AGNRs toward terrace centers, thereby altering their local growth configuration. To quantify transfer performance, we establish an automated large-area Raman analysis framework that enables pixel-wise classification based on the G mode and the radial breathing-like mode (RBLM). This approach provides a robust and scalable metric for assessing both transfer coverage and local ribbon integrity across macroscopic areas. Raman mapping uncovers strongly inhomogeneous transfer, characterized by extended regions with no detectable GNR signal and pronounced spatial variability in the RBLM-to-G intensity ratio. Transfer quality varies substantially across the sample series, with only a single high-yield outlier and most samples remaining well below 100% transfer yield. These results demonstrate that while chevron passivation locally modifies the growth configuration of 9-AGNRs on Au(788), it does not yet yield reproducible, high-quality transfer of intact aligned ribbons. The presented Raman-based analysis framework establishes a quantitative benchmark for the systematic optimization of GNR transfer strategies.

cond-mat.mtrl-sci↗

arXiv2025

Singlet Fission among two Single Molecules

Singlet fission (SF) is a photophysical process where a singlet excitation generates two triplet excited states, enhancing exciton multiplication potentially useful for solar energy conversion. Since SF typically outcompetes radiative decay, single molecule studies of SF have remained elusive. Here, we present single molecule spectroscopy of a terrylenediimide (TDI) dimer at room and cryogenic temperatures. By analysing the stream of photons emitted by single dimers, the rates of formation and decay of SF-born triplet states were determined. We report considerable static and dynamic heterogeneities of the SF process which are reflected in broad rate distributions as well as the occasional occurrence of delayed fluorescence and rate fluctuations during spin evolution. Cryogenic experiments point to the formation of a coherent multiexciton superposition state which decays into the singlet exciton from which a correlated triplet pair evolves. Our results establish single molecule spectroscopy as a new avenue into mechanistic details of the SF process which often are drowned by ensemble av-eraging.

physics.chem-ph↗

arXiv2025

Optimized Synthesis and Device Integration of Long 17-Atom-Wide Armchair Graphene Nanoribbons

Seventeen-carbon-atom-wide armchair graphene nanoribbons (17-AGNRs) are promising candidates for high-performance electronic devices due to their narrow electronic bandgap. Atomic precision in edge structure and width control is achieved through a bottom-up on-surface synthesis (OSS) approach from tailored molecular precursors in ultra-high vacuum (UHV). This synthetic protocol must be optimized to meet the structural requirements for device integration, with ribbon length being the most critical parameter. Here, we report optimized OSS conditions that produce 17-AGNRs with an average length of approximately 17 nm. This length enhancement is achieved through a gradual temperature ramping during an extended annealing period, combined with a template-like effect driven by monomer assembly at high surface coverage. The resulting 17-AGNRs are comprehensively characterized in UHV using scanning probe techniques and Raman spectroscopy. Raman measurements following substrate transfer enabled the characterization of the length distribution of GNRs on the device substrate and confirmed their stability under ambient conditions and harsh chemical environments, including acid vapors and etchants. The increased length and ambient stability of the 17-AGNRs lead to their reliable integration into device architectures. As a proof of concept, we integrate 17-AGNRs into field-effect transistors (FET) with graphene electrodes and confirm that electronic transport occurs through the GNRs. This work demonstrates the feasibility of integrating narrow-bandgap GNRs into functional devices and contributes to advancing the development of carbon-based nanoelectronics.

cond-mat.mes-hall↗

arXiv2024

Topological Woodward-Hoffmann classification for cycloadditions in polycyclic aromatic azomethine ylides

The study of cycloaddition mechanisms is central to the fabrication of extended sp2 carbon nanostructures. Reaction modeling in this context has focused mostly on putative, energetically preferred, exothermic products with limited consideration for symmetry allowed or forbidden mechanistic effects. Here, we introduce a scheme for classifying symmetry-forbidden reaction coordinates in Woodward-Hoffmann correlation diagrams. Topological classifiers grant access to the study of reaction pathways and correlation diagrams in the same footing, for the purpose of elucidating mechanisms and products of polycyclic aromatic azomethine ylide (PAMY) cycloadditions with pentacene-yielding polycyclic aromatic hydrocarbons with an isoindole core in the solid-state and on surfaces as characterized by mass spectrometry and scanning tunneling microscopy, respectively. By means of a tight-binding reaction model and density functional theory (DFT) we find topologically-allowed pathways if a product is endothermic, and topologically-forbidden if a product is exothermic. Our work unveils topological classification as a crucial element for reaction modeling for nanographene engineering, and highlights its fundamental role in the design of cycloadditions in on-surface and solid-state chemical reactions, while underscoring that exothermic pathways can be topologically-forbidden.

physics.chem-ph↗

arXiv2024

Thermal spin-crossover and temperature-dependent zero-field splitting in magnetic nanographene chains

Nanographene-based magnetism at interfaces offers an avenue to designer quantum materials towards novel phases of matter and atomic-scale applications. Key to spintronics applications at the nanoscale is bistable spin-crossover which however remains to be demonstrated in nanographenes. Here we show that antiaromatic 1,4-disubstituted pyrazine-embedded nanographene derivatives, which promote magnetism through oxidation to a non-aromatic radical are prototypical models for the study of carbon-based thermal spin-crossover. Scanning tunneling spectroscopy studies reveal symmetric spin excitation signals which evolve at Tc to a zero-energy peak, and are assigned to the transition of a S = 3/2 high-spin to a S = 1/2 low-spin state by density functional theory. At temperatures below and close to the spin-crossover Tc, the high-spin S= 3/2 excitations evidence pronouncedly different temperature-dependent excitation energies corresponding to a zero-field splitting in the Hubbard-Kanamori Hamiltonian. The discovery of thermal spin crossover and temperature-dependent zero-field splitting in carbon nanomaterials promises to accelerate quantum information, spintronics and thermometry at the atomic scale.

physics.chem-ph↗

arXiv2023

Quantifying Alignment and Quality of Graphene Nanoribbons: A Polarized Raman Spectroscopy Approach

Graphene nanoribbons (GNRs) are atomically precise stripes of graphene with tunable electronic properties, making them promising for room-temperature switching applications like field-effect transistors (FETs). However, challenges persist in GNR processing and characterization, particularly regarding GNR alignment during device integration. In this study, we quantitatively assess the alignment and quality of 9-atom-wide armchair graphene nanoribbons (9-AGNRs) on different substrates using polarized Raman spectroscopy. Our approach incorporates an extended model that describes GNR alignment through a Gaussian distribution of angles. We not only extract the angular distribution of GNRs but also analyze polarization-independent intensity contributions to the Raman signal, providing insights into surface disorder on the growth substrate and after substrate transfer. Our findings reveal that low-coverage samples grown on Au(788) exhibit superior uniaxial alignment compared to high-coverage samples, attributed to preferential growth along step edges, as confirmed by scanning tunneling microscopy (STM). Upon substrate transfer, the alignment of low-coverage samples deteriorates, accompanied by increased surface disorder. On the other hand, high-coverage samples maintain alignment and exhibit reduced disorder on the target substrate. Our extended model enables a quantitative description of GNR alignment and quality, facilitating the development of GNR-based nanoelectronic devices.

cond-mat.mtrl-sci↗

arXiv2023

MoRe Electrodes with 10-nm Nanogaps for Electrical Contact to Atomically Precise Graphene Nanoribbons

Atomically precise graphene nanoribbons (GNRs) are predicted to exhibit exceptional edge-related properties, such as localized edge states, spin polarization, and half-metallicity. However, the absence of low-resistance nano-scale electrical contacts to the GNRs hinders harnessing their properties in field-effect transistors. In this paper, we make electrical contact with 9-atom-wide armchair GNRs using superconducting alloy MoRe as well as Pd (as a reference), which are two of the metals providing low-resistance contacts to carbon nanotubes. We take a step towards contacting a single GNR by fabrication of electrodes with a needle-like geometry, with about 20 nm tip diameter and 10 nm separation. To preserve the nano-scale geometry of the contacts, we develop a PMMA-assisted technique to transfer the GNRs onto the pre-patterned electrodes. Our device characterizations as a function of bias-voltage and temperature, show a thermally-activated gate-tunable conductance in the GNR-MoRe-based transistors.

cond-mat.mes-hall↗

arXiv2023

Twisted bilayer zigzag-graphene nanoribbon junctions with tunable edge states

Stacking two-dimensional layered materials such as graphene and transitional metal dichalcogenides with nonzero interlayer twist angles has recently become attractive because of the emergence of novel physical properties. Stacking of one-dimensional nanomaterials offers the lateral stacking offset as an additional parameter for modulating the resulting material properties. Here, we report that the edge states of twisted bilayer zigzag graphene nanoribbons (TBZGNRs) can be tuned with both the twist angle and the stacking offset. Strong edge state variations in the stacking region are first revealed by density functional theory (DFT) calculations. We construct and characterize twisted bilayer zigzag graphene nanoribbon (TBZGNR) systems on a Au(111) surface using scanning tunneling microscopy. A detailed analysis of three prototypical orthogonal TBZGNR junctions exhibiting different stacking offsets by means of scanning tunneling spectroscopy reveals emergent near-zero-energy states. From a comparison with DFT calculations, we conclude that the emergent edge states originate from the formation of flat bands whose energy and spin degeneracy are highly tunable with the stacking offset. Our work highlights fundamental differences between 2D and 1D twistronics and spurs further investigation of twisted one-dimensional systems.

cond-mat.mes-hall↗

arXiv2022

Tunable quantum dots from atomically precise graphene nanoribbons using a multi-gate architecture

Atomically precise graphene nanoribbons (GNRs) are increasingly attracting interest due to their largely modifiable electronic properties, which can be tailored by controlling their width and edge structure during chemical synthesis. In recent years, the exploitation of GNR properties for electronic devices has focused on GNR integration into field-effect-transistor (FET) geometries. However, such FET devices have limited electrostatic tunability due to the presence of a single gate. Here, we report on the device integration of 9-atom wide armchair graphene nanoribbons (9-AGNRs) into a multi-gate FET geometry, consisting of an ultra-narrow finger gate and two side gates. We use high-resolution electron-beam lithography (EBL) for defining finger gates as narrow as 12 nm and combine them with graphene electrodes for contacting the GNRs. Low-temperature transport spectroscopy measurements reveal quantum dot (QD) behavior with rich Coulomb diamond patterns, suggesting that the GNRs form QDs that are connected both in series and in parallel. Moreover, we show that the additional gates enable differential tuning of the QDs in the nanojunction, providing the first step towards multi-gate control of GNR-based multi-dot systems.

cond-mat.mes-hall↗

arXiv2022

Ultimately-scaled electrodes for contacting individual atomically-precise graphene nanoribbons

Bottom-up synthesized graphene nanoribbons (GNRs) are quantum materials that can be structured with atomic precision, providing unprecedented control over their physical properties. Accessing the intrinsic functionality of GNRs for quantum technology applications requires the manipulation of single charges, spins, or photons at the level of an individual GNR. However, experimentally, contacting individual GNRs remains challenging due to their nanometer-sized width and length as well as their high density on the metallic growth substrate. Here, we demonstrate the contacting and electrical characterization of individual GNRs in a multi-gate device architecture using single-walled carbon nanotubes (SWNTs) as ultimately-scaled electrodes. The GNR-SWNT devices exhibit well-defined quantum transport phenomena, including Coulomb blockade, excited states, and Franck-Condon blockade, all characteristics pointing towards the contacting of an individual GNR. Combined with the multi-gate architecture, this contacting method opens a road for the integration of GNRs in quantum devices to exploit their topologically trivial and non-trivial nature.

cond-mat.mes-hall↗

arXiv2022

Growth optimization and device integration of narrow-bandgap graphene nanoribbons

The electronic, optical and magnetic properties of graphene nanoribbons (GNRs) can be engineered by controlling their edge structure and width with atomic precision through bottom-up fabrication based on molecular precursors. This approach offers a unique platform for all-carbon electronic devices but requires careful optimization of the growth conditions to match structural requirements for successful device integration, with GNR length being the most critical parameter. In this work, we study the growth, characterization, and device integration of 5-atom wide armchair GNRs (5-AGNRs), which are expected to have an optimal band gap as active material in switching devices. 5-AGNRs are obtained via on-surface synthesis under ultra-high vacuum conditions from Br- and I-substituted precursors. We show that the use of I-substituted precursors and the optimization of the initial precursor coverage quintupled the average 5-AGNR length. This significant length increase allowed us to integrate 5-AGNRs into devices and to realize the first field-effect transistor based on narrow bandgap AGNRs that shows switching behavior at room temperature. Our study highlights that optimized growth protocols can successfully bridge between the sub-nanometer scale, where atomic precision is needed to control the electronic properties, and the scale of tens of nanometers relevant for successful device integration of GNRs.

cond-mat.mtrl-sci↗

arXiv2022

Scaling and Statistics of Bottom-Up Synthesized Armchair Graphene Nanoribbon Transistors

Bottom-up assembled nanomaterials and nanostructures allow for the studies of rich and unprecedented quantum-related and mesoscopic transport phenomena. However, it can be difficult to quantify the correlations between the geometrical or structural parameters obtained from advanced microscopy and measured electrical characteristics when they are made into macroscopic devices. Here, we propose a strategy to connect the nanomaterial morphologies and the device performance through a Monte Carlo device model and apply it to understand the scaling trends of bottom-up synthesized armchair graphene nanoribbon (GNR) transistors. A new nanofabrication process is developed for GNR transistors with channel length down to 7 nm. The impacts of the GNR spatial distributions and the device geometries on the device performance are investigated systematically through comparison of experimental data with the model. Through this study, challenges and opportunities of transistor technologies based on bottom-up synthesized GNRs are pinpointed, paving the way to the further improvement of the GNR device performance for future transistor technology nodes.

cond-mat.mes-hall↗

arXiv2021

Optimized Graphene Electrodes for contacting Graphene Nanoribbons

Atomically precise graphene nanoribbons are a promising emerging class of designer quantum materials with electronic properties that are tunable by chemical design. However, many challenges remain in the device integration of these materials, especially regarding contacting strategies. We report on the device integration of uniaxially aligned and non-aligned 9-atom wide armchair graphene nanoribbons (9-AGNRs) in a field-effect transistor geometry using electron beam lithography-defined graphene electrodes. This approach yields controlled electrode geometries and enables higher fabrication throughput compared to previous approaches using an electrical breakdown technique. Thermal annealing is found to be a crucial step for successful device operation resulting in electronic transport characteristics showing a strong gate dependence. Raman spectroscopy confirms the integrity of the graphene electrodes after patterning and of the GNRs after device integration. Our results demonstrate the importance of the GNR-graphene electrode interface and pave the way for GNR device integration with structurally well-defined electrodes.

cond-mat.mes-hall↗

arXiv2020

Coupled spin states in armchair graphene nanoribbons with asymmetric zigzag edge extensions

Carbon-based magnetic structures promise significantly longer coherence times than traditional magnetic materials, which is of fundamental importance for spintronic applications. An elegant way of achieving carbon-based magnetic moments is the design of graphene nanostructures with an imbalanced occupation of the two sublattices forming the carbon honeycomb lattice. According to Lieb's theorem, this induces local magnetic moments that are proportional to the sublattice imbalance. Exact positioning of sublattice imbalanced nanostructures in graphene nanomaterials hence offers a route to control interactions between induced local magnetic moments and to obtain graphene nanomaterials with magnetically non-trivial ground states. Here, we show that such sublattice imbalanced nanostructures can be incorporated along a large band gap armchair graphene nanoribbon on the basis of asymmetric zigzag edge extensions, which is achieved by incorporating specifically designed precursor monomers during the bottom-up fabrication of the graphene nanoribbons. Scanning tunneling spectroscopy of an isolated and electronically decoupled zigzag edge extension reveals Hubbard-split states in accordance with theoretical predictions. Investigation of pairs of such zigzag edge extensions reveals ferromagnetic, antiferromagnetic or quenching of the magnetic interactions depending on the relative alignment of the asymmetric edge extensions. Moreover, a ferromagnetic spin chain is demonstrated for a periodic pattern of zigzag edge extensions along the nanoribbon axis. This work opens a route towards the design and fabrication of graphene nanoribbon-based spin chains with complex magnetic ground states.

cond-mat.mes-hall↗

arXiv2019

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 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.

cond-mat.mes-hall↗

arXiv2019

Band Gap of Atomically Precise Graphene Nanoribbons as a Function of Ribbon Length and Termination

We study the band gap of finite $N_A=7$ armchair graphene nanoribbons (7-AGNRs) on Au(111) through scanning tunneling microscopy/spectroscopy combined with density functional theory calculations. The band gap of 7-AGNRs with lengths of 6 nm and more is converged to within 0.1 eV of its bulk value of 2.3 eV, while the band gap opens by several hundred meV in very short 7-AGNRs. The termination has a significant effect on the band gap, doubly hydrogenated termini yielding a lower band gap than singly hydrogenated ones.

cond-mat.mes-hall↗

arXiv2019

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 scanning tunneling microscopy/spectroscopy and non-contact atomic force microscopy, complemented by density-functional theory calculations. These polymers present a low band gap when adsorbed on Au(111). Moreover, their pro-nounced antiaromaticity and radical character, elucidated by ab initio calculations, make them promising candidates for applications in electronics and spintronics. Further, they provide a rich playground to explore magnetism in low-dimensional organic nanomaterials.

cond-mat.mtrl-sci↗