Probing Spin-Dependent Ballistic Charge Transport at Single-Nanometer Length Scales.

The coherent transport of charge and spin is a key requirement of future devices for quantum computing and communication. Scattering at defects or impurities may significantly reduce the coherence of quantum-mechanical states, thereby affecting the device functionality. While numerous methods exist to experimentally assess charge transport, the real-space detection of a material's ballistic spin transport properties with nanometer resolution remains a challenge. Here we report on a novel approach that utilizes a combination of spin-polarized scanning tunneling microscopy (SP-STM) and the recently introduced molecular nanoprobe (MONA) technique. It relies on the local injection of spin-polarized charge carriers from a magnetic STM tip and their detection by a single surface-deposited phthalocyanine molecule via reversible electron-induced tautomerization events. Based on the particular electronic structure of the Rashba alloy BiAg2, which is governed by a spin-momentum-locked surface state, we prove that the current direction inverses upon tip magnetization reversal.

Controlled Formation of Porous 2D Lattices from C3 -symmetric Ph6 -Me-Tribenzotriquinacene-OAc3.

The on-surface self-assembly of molecules to form holey nanographenes is a promising approach to control the properties of the resulting 2D lattice. Usually, planar molecules are utilized to prepare flat, structurally confined molecular layers, with only a few recent examples of warped precursors. However, control of the superstructures is limited thus far. Herein, we report the temperature-controlled self-assembly of a bowl-shaped, acetylated C3 -symmetric hexaphenyltribenzotriquinacene derivative on Cu(111). Combining scanning tunneling microscopy (STM) and density functional theory (DFT) confirms the formation of highly differing arrangements starting with π-stacked bowl-to-bowl dimers at low coverage at room temperature via chiral honeycomb structures, an intermediate trigonal superstructure, followed by a fully carbon-based, flattened hexagonal superstructure formed by on-surface deacetylation, which is proposed as a precursor for holey graphene networks with unique defect structures.

Real-space resolved surface reactions: deprotonation and metalation of phthalocyanine.

Upon deposition on a surface, molecules can undergo a plethora of changes, such as reactions with adsorbates and surface atoms and catalytic decomposition. Since different reaction pathways may coexist, spatially averaging techniques can be insufficient for the characterization and distinction of all on-surface products. Here, we present a study of single phthalocyanine molecules on a Cu(111) surface which was performed using high-resolution low-temperature STM. Upon deposition of metal-free H2Pc, we can identify three distinct molecular species. A thorough investigation reveals that temperature-driven on-surface reactions partially convert H2Pc into H0Pc and CuPc. The individual species are differentiated by their topographic appearance and can unambiguously be identified by their STM-induced rotational behavior. While H2Pc shows a switching between two orientations at low energies, a third orientation can be observed above E > 800 meV, which is induced by tautomerization. Around the Fermi level, the rotational behavior is asymmetric, owing to the excitation of vibrational modes in unoccupied states whereas resonant tunneling occurs in occupied states. A two-step deprotonation of H2Pc confirms that the second species is H0Pc. By comparison with CuPc evaporated on Cu(111), we unambiguously reveal that the third species is indeed CuPc, which exhibits an exceptionally low threshold for rotational switching accompanied by an asymmetric behavior around the Fermi level. Varying the post-annealing temperature, we found a sharp threshold for the H2Pc → CuPc on-surface metalation at around 100 °C. In contrast, the competing process of thermal decomposition from H2Pc to H0Pc only increases weakly.

Anisotropic coupling of individual vibrational modes to a Cu(110) substrate.

We present a study on the excitation of individual vibrational modes with ballistic charge carriers propagating along the Cu(110) surface. By means of the molecular nanoprobe technique, where the reversible switching of a molecule-in this case tautomerization of porphycene-is utilized to detect excitation events, we reveal anisotropic coupling of two distinct vibrational modes to the substrate. The N-H bending mode, excited below |E| ≈ 376 meV, exhibits maxima perpendicular to the rows of the Cu(110) substrate and minima along the rows. In contrast, the N-H stretching mode, excited above |E| ≈ 376 meV, displays maxima along the rows and is constant otherwise. This inversion of the anisotropy reflects the orthogonality between the N-H bending and stretching mode. Additionally, we observe an energy-dependent asymmetry in the propagation direction of charge carriers injected into the Cu(110) surface state. Hereby, the anisotropic band structure results in a correlation between the group velocity and the tunneling probability into electronic states of the substrate.

Molecular Chains: Arranging and Programming Logic Gates.

One particularly fascinating vision for charge-operated devices is the controlled assembly of structures from single surface-deposited molecules. Here, we report on the assembly of linear clusters that consist of phthalocyanine (H2Pc) molecules on a Ag(111) surface. The molecules are imaged as well as manipulated with a low-temperature scanning tunneling microscope (STM). Upon deprotonation of every second H2Pc, the resulting HPc molecule exhibits an isomeric bistability which can be used as inputs in logic gates. Combining our STM measurements with density functional theory calculations we show that the HPc isomers exhibit a repulsive electrostatic interaction with adjacent H2Pc molecules which, due to the asymmetric charge distribution on HPc, results in a counterclockwise or clockwise molecule tilt of the latter, thereby defining the logic 0 and 1 of the output. It is shown that information can be relayed along molecule chains over distances equivalent to at least nine molecules.

Anisotropic Ballistic Transport Revealed by Molecular Nanoprobe Experiments.

Atomic-scale charge transport properties are not only of significant fundamental interest but also highly relevant for numerous technical applications. However, experimental methods that are capable of detecting charge transport at the relevant single-digit nanometer length scale are scarce. Here we report on molecular nanoprobe experiments on Pd(110), where we use the charge carrier-driven switching of a single cis-2-butene molecule to detect ballistic transport properties over length scales of a few nanometers. Our data demonstrate a striking angular dependence with a dip in the charge transport along the [11[over ¯]0]-oriented atomic rows and a peak in the transverse [001] direction. The narrow angular width of both features and distance-dependent measurements suggest that the nanometer-scale ballistic transport properties of metallic surfaces are significantly influenced by the atomic structure.

Analyzing the Wave Nature of Hot Electrons with a Molecular Nanoprobe.

We report on a novel method, the molecular nanoprobe (MONA) technique, which allows us to measure the nanoscale quasiparticle transport between two arbitrary surface points. In these experiments, hot electrons are injected into the sample surface from the probe tip of a scanning tunneling microscope (STM) and detected by tautomerization switching events of a single deprotonated phthalocyanine (H2Pc) molecule. By making use of atom-by-atom-engineered interferometers on a Ag(111) surface, we demonstrate that the quantum-mechanical wave nature of hot electrons leads to characteristic oscillations of the molecule tautomerization probability. Two interferometers can be combined to build an energy-dependent selector, which allows it to selectively switch one out of two molecules without changing the position of the STM tip. The MONA technique is compared with conventional d I/d U measurements, where the injection and detection point of hot electrons is intrinsically tied to the same tip location.

Remote Single-Molecule Switching: Identification and Nanoengineering of Hot Electron-Induced Tautomerization.

Molecular electronics where single molecules perform basic functionalities of digital circuits is a fascinating concept that one day may augment or even replace nowadays semiconductor technologies. The tautomerization of molecules, that is, the bistable functional position of hydrogen protons within an organic frame, has recently been intensively discussed as a potential avenue toward nanoscale switches. It has been shown that tautomerization can be triggered locally or nonlocally, that is, by a scanning tunneling microscope (STM) tip positioned directly above or in close vicinity to the molecule. Whereas consensus exists that local switching is caused by inelastic electrons that excite vibrational molecular modes, the detailed processes responsible for nonlocal tautomerization switching and, even more important in the context of this work, methods to control, engineer, and potentially utilize this process are largely unknown. Here, we demonstrate for dehydrogenated H2Pc molecules on Ag(111) how to controllably decrease or increase the probability of nonlocal, hot electron-induced tautomerization by atom-by-atom designed Ag nanostructures. We show that Ag atom walls act as potential barriers that exponentially damp the hot electron current between the injection point and the molecule, reducing the switching probability by up to 83% for a four-atom wide wall. By placing the molecule in one and the STM tip in the other focal point of an elliptical nanostructure, we could coherently focus hot electrons onto the molecule that led to an almost tripled switching probability. Furthermore, single and double slit experiment based on silver atom structures were used to characterize the spatial extension of hot electron packets. The absence of any detectable interference pattern suggests that the coherence length of the hot electrons that trigger tautomerization processes is rather short. Our results demonstrate that the tautomerization switching of single molecules can remotely be controlled by utilizing suitable nanostructures and may pave the way for designing new tautomerization-based switches.

Imprinting Directionality into Proton Transfer Reactions of an Achiral Molecule.

Directionality is key for the functionality of molecular machines, which is often achieved by built-in structural chiralities. Here, we present a scanning tunneling microscopy study of achiral H2Pc and HPc molecules that acquire chirality by adsorption onto a Ag(100) surface. The adsorption-geometry-induced chirality is caused by a -29° (+29°) rotation of the molecules with respect to the [011] substrate direction, resulting in tautomerization processes that preferentially occur in a clockwise (counterclockwise) direction. The directionality is found to be independent of the particular energy and location of charge carrier injection. In contrast to built-in structural chiralities that are fixed by the molecular structure, the direction of proton motion in HPc on Ag(100) can be inverted by a rotation of the molecule on the substrate.