Single-Spin Sensing: A Molecule-on-Tip Approach.

Magnetometry plays a pivotal role in addressing the requirements of ultradense storage technology and overcoming challenges associated with downscaled spin qubits. A promising approach for atomic-scale single-spin sensing involves utilizing a magnetic molecule as a spin sensor, although such a realization is still in its early stages. To tackle this challenge and underscore the potential of this method, we combined a nickelocene molecule with scanning tunneling microscopy to perform versatile spin-sensitive imaging of magnetic surfaces. We investigated model Co islands on Cu(111) of different thicknesses having variable magnetic properties. Our method demonstrates robustness and reproducibility, providing atomic-scale sensitivity to spin polarization and magnetization orientation, owing to a direct exchange coupling between the nickelocene-terminated tip and the Co surfaces. We showcase the accessibility of magnetic exchange maps using this technique, revealing unique signatures in magnetic corrugation, which are well described by computed spin-density maps. These advancements significantly improve our capacity to probe and visualize magnetism at the atomic level.

Submolecular-scale control of phototautomerization.

Optically activated reactions initiate biological processes such as photosynthesis or vision, but can also control polymerization, catalysis or energy conversion. Methods relying on the manipulation of light at macroscopic and mesoscopic scales are used to control on-surface photochemistry, but do not offer atomic-scale control. Here we take advantage of the confinement of the electromagnetic field at the apex of a scanning tunnelling microscope tip to drive the phototautomerization of a free-base phthalocyanine with submolecular precision. We can control the reaction rate and the relative tautomer population through a change in the laser excitation wavelength or through the tip position. Atomically resolved tip-enhanced photoluminescence spectroscopy and hyperspectral mapping unravel an excited-state mediated process, which is quantitatively supported by a comprehensive theoretical model combining ab initio calculations with a parametric open-quantum-system approach. Our experimental strategy may allow insights in other photochemical reactions and proof useful to control complex on-surface reactions.

Energy funnelling within multichromophore architectures monitored with subnanometre resolution.

The funnelling of energy within multichromophoric assemblies is at the heart of the efficient conversion of solar energy by plants. The detailed mechanisms of this process are still actively debated as they rely on complex interactions between a large number of chromophores and their environment. Here we used luminescence induced by scanning tunnelling microscopy to probe model multichromophoric structures assembled on a surface. Mimicking strategies developed by photosynthetic systems, individual molecules were used as ancillary, passive or blocking elements to promote and direct resonant energy transfer between distant donor and acceptor units. As it relies on organic chromophores as the elementary components, this approach constitutes a powerful model to address fundamental physical processes at play in natural light-harvesting complexes.

Single-molecule tautomerization tracking through space- and time-resolved fluorescence spectroscopy.

Tautomerization, the interconversion between two constitutional molecular isomers, is ubiquitous in nature1, plays a major role in chemistry2 and is perceived as an ideal switch function for emerging molecular-scale devices3. Within free-base porphyrin4, porphycene5 or phthalocyanine6, this process involves the concerted or sequential hopping of the two inner hydrogen atoms between equivalent nitrogen sites of the molecular cavity. Electronic and vibronic changes6 that result from this NH tautomerization, as well as details of the switching mechanism, were extensively studied with optical spectroscopies, even with single-molecule sensitivity7. The influence of atomic-scale variations of the molecular environment and submolecular spatial resolution of the tautomerization could only be investigated using scanning probe microscopes3,8-11, at the expense of detailed information provided by optical spectroscopies. Here, we combine these two approaches, scanning tunnelling microscopy (STM) and fluorescence spectroscopy12-15, to study the tautomerization within individual free-base phthalocyanine (H2Pc) molecules deposited on a NaCl-covered Ag(111) single-crystal surface. STM-induced fluorescence (STM-F) spectra exhibit duplicate features that we assign to the emission of the two molecular tautomers. We support this interpretation by comparing hyper-resolved fluorescence maps15-18(HRFMs) of the different spectral contributions with simulations that account for the interaction between molecular excitons and picocavity plasmons19. We identify the orientation of the molecular optical dipoles, determine the vibronic fingerprint of the tautomers and probe the influence of minute changes in their atomic-scale environment. Time-correlated fluorescence measurements allow us to monitor the tautomerization events and to associate the proton dynamics to a switching two-level system. Finally, optical spectra acquired with the tip located at a nanometre-scale distance from the molecule show that the tautomerization reaction occurs even when the tunnelling current does not pass through the molecule. Together with other observations, this remote excitation indicates that the excited state of the molecule is involved in the tautomerization reaction path.

Vibronic Spectroscopy with Submolecular Resolution from STM-Induced Electroluminescence.

A scanning tunneling microscope is used to generate the electroluminescence of phthalocyanine molecules deposited on NaCl/Ag(111). Photon spectra reveal an intense emission line at ≈1.9 eV that corresponds to the fluorescence of the molecules, and a series of weaker redshifted lines. Based on a comparison with Raman spectra acquired on macroscopic molecular crystals, these spectroscopic features can be associated with the vibrational modes of the molecules and provide a detailed chemical fingerprint of the probed species. Maps of the vibronic features reveal submolecularly resolved structures whose patterns are related to the symmetry of the probed vibrational modes.

Efficient Spin-Flip Excitation of a Nickelocene Molecule.

Inelastic electron tunneling spectroscopy (IETS) within the junction of a scanning tunneling microscope (STM) uses current-driven spin-flip excitations for an all-electrical characterization of the spin state of a single object. Usually decoupling layers between the single object, atom or molecule, and the supporting surface are needed to observe these excitations. Here we study the surface magnetism of a sandwich nickelocene molecule (Nc) adsorbed directly on Cu(100) by means of X-ray magnetic circular dichroism (XMCD) and density functional theory (DFT) calculations and show with IETS that it exhibits an exceptionally efficient spin-flip excitation. The molecule preserves its magnetic moment and magnetic anisotropy not only on Cu(100), but also in different metallic environments including the tip apex. By taking advantage of this robusteness, we are able to functionalize the microscope tip with a Nc, which can be employed as a portable source of inelastic excitations as exemplified by a double spin-flip excitation process.

Broadband transient dichroism spectroscopy in chiral molecules.

We perform time-resolved broadband transmission ellipsometry using the ultrafast pump-probe technique in an original setup. Our setup allows us to measure, over a wide spectral range, the optical rotary dispersion of the sample or, when needed, its circular dichroism by adding a broadband quarter-wave plate. While our experiment has been designed to study the transient states in chiral molecules, it performs sufficiently well to also characterize the ground state.

External stimulus driven variable-step grating in a nematic elastomer.

We report on the creation of micro-patterns in an oriented nematic elastomer (an artificial muscle material) by photopolymerization of surface aligned nematic liquid crystal monomers. We demonstrate that microscopic techniques are able to create accurate patterns in rubber-like liquid crystal materials. Two approaches, based on one and two-photon excitations respectively, are implemented using a microscope-based setup. Due to its high spatial selectivity, the two-photon excitation mode yields finer patterns. Benefitting from the intrinsic, thermally-induced, contractile properties of the material, gratings with variable steps in response to temperature changes were fabricated.