single-electron tunneling
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The interplay between chirality and magnetism is a source of fascination among scientists for over a century. In recent years, chirality-induced spin selectivity (CISS) has attracted renewed interest. It is observed that electron transport through layers of homochiral molecules leads to a significant spin polarization of several tens of percent. Despite the abundant experimental evidence gathered through mesoscopic transport measurements, the exact mechanism behind CISS remains elusive. This study reports spin-selective electron transport through single helical aromatic hydrocarbons that are sublimed in vacuo onto ferromagnetic cobalt surfaces and examined with spin-polarized scanning tunneling microscopy (SP-STM) at a temperature of 5 K. Direct comparison of two enantiomers under otherwise identical conditions revealed magnetochiral conductance asymmetries of up to 50% when either the molecular handedness is exchanged or the magnetization direction of the STM tip or Co substrate is reversed. Importantly, the results rule out electron-phonon coupling and ensemble effects as primary mechanisms responsible for CISS.
- Klíčová slova
- CISS effect, chirality, ferromagnetic substrate, scanning probe microscopy, single‐molecule studies,
- Publikační typ
- časopisecké články MeSH
Helicenes represent an important class of chiral organic material with promising optoelectronic properties. Hence, functionalization of surfaces with helicenes is a key step towards new organic material devices. This review presents different aspects of adsorption and modification of metal surfaces with different helicene species. Topics addressed are chiral crystallization, that is, 2D conglomerate versus racemate crystallization, breaking of mirror-symmetry in racemates, chirality-induced spin selectivity, and stereoselective on-surface chemistry.
- Klíčová slova
- CISS, helicenes, on‐surface chemistry, scanning tunneling microscopy, surface science,
- Publikační typ
- časopisecké články MeSH
- přehledy MeSH
We use inelastic electron tunneling spectroscopy (IETS) first-principles simulations to identify and characterize the different vibrational modes of single conjugated molecules bonded to Au metal electrodes. The molecules are polyphenyls (with 1 to 4 benzene units) bonded to Au via highly conducting direct Au-C bonds. The short molecule shows near resonant elastic transmission, with a crossover to tunneling for the longer backbones. The calculated inelastic spectra exhibit dips in the IETS signal of the short molecule and peaks for the longer molecules. We characterize the symmetry of vibrational modes and scattering states and discuss the changes with increasing length, where the inelastic signal of different modes can be amplified, quenched or present a crossover as more benzene units are added to the molecular backbone. This analysis rationalizes the observed trends as a function of molecular length and illustrates the role of electronic and vibrational properties on Au-C bonded molecular junctions.
- Publikační typ
- časopisecké články MeSH
Molecular radicals are efficient electroluminescent emitters due to the spin multiplicity of their electronic states. The excited states often exhibit a complex composition with multiple significant electronic configurations, which are essential for their optoelectronic properties but difficult to probe directly. Here we use light-scanning tunneling microscopy to investigate such an excited state by visualizing the response of a single radical molecule to a laser excitation. We observe characteristic atomic-scale spatial photocurrent patterns that can be tuned by applied bias voltage. We interpret these patterns as resulting from decay of an excited doublet state through sequential electron transfers with the tip and the substrate. The relative contributions of two dominating electronic configurations involved in this excited state are tuned by the applied voltage. This approach thus allows for disentangling the components of multiconfigurational excited states in single molecules.
- Publikační typ
- časopisecké články MeSH
The fast growth of hydrogen usage as a clean fuel in civil applications such as transportation, space technology, etc. highlights the importance of the reliable detection of its leakage and accumulation under explosion limit by sensors with a low power consumption at times when there is no accumulation of hydrogen in the environment. In this research, a new and efficient mechanism is presented for hydrogen detection-using the Coulomb blockade effect in a well-arranged 2D array of palladium nano-islands-which can operate at room temperature. We demonstrated that under certain conditions of size distribution and the regularity of palladium nano-islands, with selected sizes of 1.7, 3 and 6.1 nm, the blockade threshold will appear in current-voltage (IV) characteristics. In reality, it will be achieved by the inherent uncertainty in the size of the islands in nano-scale fabrication or by controlling the size of nanoparticles from 1.7 to 6.1 nm, considering a regular arrangement of nanoparticles that satisfies single-electron tunneling requirements. Based on the simulation results, the threshold voltage is shifted towards lower ones due to the expansion of Pd nanoparticles exposed to the environment with hydrogen concentrations lower than 2.6%. Also, exploring the features of the presented structure as a gas sensor, provides robustness against the Gaussian variation in nano-islands sizes and temperature variations. Remarkably, the existence of the threshold voltage in the IV curve and adjusting the bias voltage below this threshold leads to a drastic reduction in power consumption. There is also an improvement in the minimum detectable hydrogen concentration as well as the sensor response.
- Klíčová slova
- Coulomb blockade threshold, hydrogen gas sensor, palladium nanoparticles, room temperature, single-electron tunneling,
- Publikační typ
- časopisecké články MeSH
Single-molecule conductance in a series of extended viologen molecules was measured at room temperature using a gold-molecule-gold scanning tunneling microscopy break junction arrangement. Conductance values for individual molecules change from 4.8 ± 1.2 nS for the shortest compound to 2.9 ± 1.0 nS for the compound with six repeating units and length of 11 nm. The latter value is almost 3 orders of magnitude higher than that reported for all-carbon-based aromatic molecular wires of comparable length. On the basis of the length of the molecules, an attenuation factor of only 0.06 ± 0.004 nm(-1) (0.006 ± 0.0004 Å(-1)) was obtained. To the best of our knowledge, this is the smallest value reported for the conductance attenuation in a series of molecular wires.
- Klíčová slova
- electron transfer, extended viologens, molecular wires, scanning tunneling microscopy break junction, single molecule conductance,
- Publikační typ
- časopisecké články MeSH
Triangulene and its homologues are promising building blocks for high-spin low-dimensional networks with long-range magnetic order. Despite the recent progress in the synthesis and characterization of coupled triangulenes, key parameters such as the number of organic linking units or their dihedral angles remain scarce, making further studies crucial for an essential understanding of their implications. Here, we investigate the synthesis and reactivity of two triangulene dimers linked by two (Dimer 1) or one (Dimer 2) para-biphenyl units, respectively, on a metal surface in an ultra-high vacuum environment. First-principles calculations and model Hamiltonians reveal how spin excitation and radical character depend on the rotation of the para-biphenyl units. Comprehensive scanning tunneling microscopy (STM) in combination with density functional theory (DFT) calculations confirm the successful formation of Dimer 1 on Au(111). Non-contact atomic force microscopy (nc-AFM) measurements resolve the twisted conformation of the linking para-biphenyl units for Dimer 1. On the contrary, the inherent flexibility of Dimer 2 induces the planarization of the para-biphenyl, resulting in the spontaneous formation of two additional five-membered rings per dimer connected by a single C-C bond (Dimers 2'). Furthermore, scanning tunneling spectroscopy (STS) measurements confirm the antiferromagnetic (S=0) coupling of the observed dimers, underscoring the critical influence of dihedral angles and structural flexibility of the linking units in π-electron magnetic nanostructures.
- Klíčová slova
- open-shell character, scanning tunneling microscopy, surface chemistry, triangulenes, π-electron magnetism,
- Publikační typ
- časopisecké články MeSH
We investigate electroluminescence of single molecular emitters on NaCl on Ag(111) and Au(111) with submolecular resolution in a low-temperature scanning probe microscope with tunneling current, atomic force, and light detection capabilities. The role of the tip state is studied in the photon maps of a prototypical emitter, zinc phthalocyanine (ZnPc), using metal and CO-metal tips. CO-functionalization is found to have an impact on the resolution and contrast of the photon maps due to the localized overlap of the p-orbitals on the tip with the molecular orbitals of the emitter. The possibility of using the same CO-functionalized tip for tip-enhanced photon detection and high resolution atomic force is demonstrated. We study the electroluminescence of ZnPc, induced by charge carrier injection at sufficiently high bias voltages. We propose that the distinct level alignment of the ZnPc frontier orbitals with the Au(111) and Ag(111) Fermi levels governs the primary excitation mechanisms as the injection of electrons and holes from the tip into the molecule, respectively. These findings put forward the importance of the tip status in the photon maps and contribute to a better understanding of the photophysics of organic molecules on surfaces.
High-precision molecular manipulation techniques are used to control the distance between radical molecules on superconductors. Our results show that the molecules can host single electrons with a spin 1/2. By changing the distance between tip and sample, a quantum phase transition from the singlet to doublet ground state can be induced. Due to local screening and charge redistribution, we observe either charged or neutral molecules, which couple in a sophisticated way, showing quantum spin behavior that deviates from the classical spins. Dimers at different separations show multiple Yu-Shiba-Rusinov peaks in tunneling spectroscopy of varying intensity, which are in line with the superconducting two-impurity Anderson model, where singlet (S = 0) and doublet (S = 1/2) ground states are found. The assembly of chains of 3, 4, and 5 molecules shows alternating charge patterns, where the edge molecules always host a charge/spin. The tetramer is observed in two configurations, where the neutral site is moved by one position. We show that these two configurations can be switched by the action of the probing tip in a nondestructive manner, demonstrating that the tetramer is an information unit, based on single-electron charge reorganization.
- Klíčová slova
- Yu-Shiba-Rusinov states, molecular manipulation, radical molecules, scanning tunneling microscopy, spin switch, superconductors,
- Publikační typ
- časopisecké články MeSH
Electron donor-acceptor molecules are of outstanding interest in molecular electronics and organic solar cells for their intramolecular charge transfer controlled via electrical or optical excitation. The preservation of their electronic character in the ground state upon adsorption on a surface is cardinal for their implementation in such single-molecule devices. Here, we investigate by atomic force microscopy and scanning tunneling microscopy a prototypical system consisting of a π-conjugated tetrathiafulvalene-fused dipyridophenazine molecule adsorbed on thin NaCl films on Cu(111). Depending on the adsorption site, the molecule is found either in a nearly undisturbed free state or in a bound state. In the latter case, the molecule adopts a specific adsorption site, leading to the formation of a chelate complex with a single Na+ alkali cation pulled out from the insulating film. Although expected to be electronically decoupled, the charge distribution of the complex is drastically modified, leading to the loss of the intrinsic donor-acceptor character. The chelate complex formation is reversible with respect to lateral manipulations, enabling tunable donor-acceptor molecular switches activated by on-surface coordination.
