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.

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.

Jahn-Teller Splitting in Single Adsorbed Molecules Revealed by Isospin-Flip Excitations.

Scanning tunneling spectroscopy measurements of Mn phthalocyanine (MnPc) molecules adsorbed on (sqrt[3]×sqrt[3]) surface alloys show single inelastic steps at exclusively positive or negative bias strongly depending on the tip position. This is in contrast to conventional molecular excitation thresholds, which are independent of the current direction and therefore always occur at both positive and negative bias. This polarity selectivity is found to coincide with the spatial distribution of occupied and empty orbitals. Because of the interaction with the substrate, charge transfer into the doubly degenerate d_{π} orbitals of MnPc takes place. The resulting Jahn-Teller effect lifts the degeneracy and leads to an isospin- or pseudospin-flip excitation, the inelastic analogue of an orbital Kondo resonance.

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.

Magnetic Ground State Stabilized by Three-Site Interactions: Fe/Rh(111).

We report the direct observation of a theoretically predicted magnetic ground state in a monolayer Fe on Rh(111), which is referred to as an up-up-down-down (↑↑↓↓) double-row-wise antiferromagnetic spin structure, using spin-polarized scanning tunneling microscopy. This exotic phase, which exists in three orientational domains, is revealed by experiments with magnetic probe tips performed in external magnetic fields. It is shown that a hitherto unconsidered four-spin-three-site beyond-Heisenberg interaction distinctly contributes to the spin coupling of atoms with S≥1 spins. The observation of the ↑↑↓↓ order substantiates the presence of higher-order, in particular, three-site interactions, in thin magnetic films of itinerant magnets.

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.

Breaking Degeneracy of Tautomerization-Metastability from Days to Seconds.

We present a detailed study of the tautomerization, that is, the switching of hydrogen protons, between different sites in the molecular frame of phthalocyanine (H2Pc) on a Ag(111) substrate by means of scanning tunneling microscopy (STM) and STM-based pump-and-sample techniques. Our data reveal that the symmetry mismatch between the substrate and the molecular frame lifts the energetic degeneracy of the two H2Pc tautomers. Their energy difference is so large that only one tautomer can be found in the ground state. Tip-induced tautomerization was triggered at sufficiently high bias voltages. The excited metastable H2Pc tautomer was found to exhibit a lifetime of at least several days, as derived from the fact that the molecule did not change back to the ground state within experimentally accessible time scales as long as noninvasive tunneling parameters were used to probe the state of the molecule. By the controlled removal of a hydrogen proton from the molecule, a four-level system was created. Pump-and-sample experiments reveal that the lifetime of the metastable positions amounts to seconds only. Current- and bias-dependent studies indicate that the presence of the STM tip modifies the potential barrier, thereby allowing for a controlled tuning of the metastable tautomer's lifetime.

Coexistence of charge and ferromagnetic order in fcc Fe.

Phase coexistence phenomena have been intensively studied in strongly correlated materials where several ordered states simultaneously occur or compete. Material properties critically depend on external parameters and boundary conditions, where tiny changes result in qualitatively different ground states. However, up to date, phase coexistence phenomena have exclusively been reported for complex compounds composed of multiple elements. Here we show that charge- and magnetically ordered states coexist in double-layer Fe/Rh(001). Scanning tunnelling microscopy and spectroscopy measurements reveal periodic charge-order stripes below a temperature of 130 K. Close to liquid helium temperature, they are superimposed by ferromagnetic domains as observed by spin-polarized scanning tunnelling microscopy. Temperature-dependent measurements reveal a pronounced cross-talk between charge and spin order at the ferromagnetic ordering temperature about 70 K, which is successfully modelled within an effective Ginzburg-Landau ansatz including sixth-order terms. Our results show that subtle balance between structural modifications can lead to competing ordering phenomena.

Relevance of hybridization and filling of 3d orbitals for the Kondo effect in transition metal phthalocyanines.

Magnetic organic molecules, such as 3d transition metal phthalocyanines (TMPc), exhibit properties which make them promising candidates for future applications in magnetic data storage or spin-based data processing. Due to their small size, however, TMPc molecules are prone to quantum effects. For example, the interaction of uncompensated molecular spins with conduction electrons of the substrate may lead to the formation of a many-body singlet state, which gives rise to the so-called Kondo effect. Although the Kondo effect of TMPc molecules has been the object of several investigations, a consistent picture to describe under which conditions a Kondo state is formed is still missing. Here, we study the Kondo properties of MnPc on Ag(001) by means of the low-temperature scanning tunneling spectroscopy (LT-STS) measurements. Differential conductance dI/dU spectra reveal a zero-bias peak that is localized on the Mn ion site. Ab initio calculations combined with a many-body treatment of the multiorbital interaction show that the local Hund coupling favors the high-spin configuration on the 3d shell of the central TM atom. Therefore, each orbital gets close to its individual half-filling creating the necessary condition for many of the 3d orbitals to contribute to the observed Kondo resonance. This, however, happens only for the 3dz(2) orbital, whose hybridization to the substrate is much stronger than for the other orbitals thanks to its shape and its orientation.