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Regulating the Interactions of Adsorbates on Surfaces by Scanning Tunneling Microscopy Manipulation

Wiley
ChemPhysChem
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Abstract

Scanning tunneling microscopy (STM) manipulation has received wide attention in the surface science community since the pioneering work of Eigler to construct surface nanostructures in an atom by atom fashion. Lots of scientists have been inspired and devoted to study the surface issues with the help of STM manipulations and great achievements have been obtained. In this Minireview, we mainly describe the recent progress in applying STM manipulations to regulate the inter-adsorbate and adsorbate–substrate interactions on solid surfaces. It was shown that this technique could not only differentiate intermolecular interactions but also construct molecular nanostructures by regulating different kinds of inter-adsorbate interactions or adsorbate–substrate interactions.

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Control on the formation of a two-dimensional polymer could be achieved in two different ways. Manipulation with the tip of a scanning tunneling microscope allowed for assigning the localization of the polymerization reaction. Additionally, electron irradiation could accelerate greatly the reaction kinetics.
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The fabrication of large molecular devices, directly on surfaces in UHV conditions, by covalent coupling of smaller precursors has become in the past years an attractive solution for Molecular Electronics. This review presents the state-of-the-art and an analysis of the potential of this new field, from Ullmann type C-C coupling, cyclodehydrogenation, and reactions involving heteroelements to 2D polymerisation on insulating thin films. Mechanistic insights are also mentioned, giving preliminary explanations on the influence of the substrate and the 2D confinement. Potential perspectives for further developments are then evoked.
Article
Key to single-molecule electronics is connecting functional molecules to each other using conductive nanowires. This involves two issues: how to create conductive nanowires at designated positions, and how to ensure chemical bonding between the nanowires and functional molecules. Here, we present a novel method that solves both issues. Relevant functional molecules are placed on a self-assembled monolayer of diacetylene compound. A probe tip of a scanning tunneling microscope is then positioned on the molecular row of the diacetylene compound to which the functional molecule is adsorbed, and a conductive polydiacetylene nanowire is fabricated by initiating chain polymerization by stimulation with the tip. Since the front edge of chain polymerization necessarily has a reactive chemical species, the created polymer nanowire forms chemical bonding with an encountered molecular element. We name this spontaneous reaction "chemical soldering". First-principles theoretical calculations are used to investigate the structures and electronic properties of the connection. We demonstrate that two conductive polymer nanowires are connected to a single phthalocyanine molecule. A resonant tunneling diode formed by this method is discussed.
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Stacked up: Use of scanning tunneling microscopy allows manipulation of the upper porphyrin of tris(porphyrinato) cerium triple-decker complexes, which are obtained by a new synthetic route on a smooth Ag(111) surface (see picture).
Article
Molecules that undergo reversible isomerization between trans and cis states, typically upon illumination with light at appropriate wavelengths, represent an important class of molecular switches. In this combined scanning tunneling microscopy (STM) and high-resolution electron energy loss spectroscopy (HREELS) study, we report on self-assembled arrays of imine derivatives on a Au(111) surface. Most of the molecules are found in the trans state after deposition at room temperature, but many of them change their conformation upon heating, which we assign to switching to the cis state. As for many molecular switches, the trans isomer is the energetically more stable compound in solution, resulting in thermal cis to trans relaxation upon sufficient heating. On the surface, however, the number of cis isomers increases with temperature, pointing toward an "inverted" thermal isomerization behavior. The reason for this surface-mediated effect could be a stronger coupling, as compared to the trans state, of the central imine part of the molecule to the gold surface, which is sterically only possible in the cis state.
Article
Quantum states of a trinaphthylene molecule were manipulated by putting its naphthyl branches in contact with single Au atoms. One Au atom carries 1-bit of classical information input that is converted into quantum information throughout the molecule. The Au-trinaphthylene electronic interactions give rise to measurable energy shifts of the molecular electronic states demonstrating a NOR logic gate functionality. The NOR truth table of the single molecule logic gate was characterized by means of scanning tunnelling spectroscopy.
Article
We present scanning tunneling microscopy (STM)-based single-molecule synthesis of linear metal-ligand complexes starting from individual metal atoms (iron or nickel) and organic molecules (9,10-dicyanoanthracene) deposited on an ultrathin insulating film. We directly visualize the frontier molecular orbitals by STM orbital imaging, from which, in conjunction with detailed density functional theory calculations, the electronic structure of the complexes is inferred. Our studies show how the order of the molecular orbitals and the spin-state of the complex can be engineered through the choice of the metal atom. The high-spin iron complex has a singly occupied delocalized orbital with a large spin-splitting that points to the use of these engineered complexes as modular building blocks in molecular spintronics.
Article
The development of methods for controlling the motion and arrangement of molecules adsorbed on a metal surface would provide a powerful tool for the design of molecular electronic devices. Recently, metal phthalocyanines (MPc) have been extensively considered for use in such devices. Here we show that applied electric fields can be used to turn off the diffusivity of iron phthalocyanine (FePc) on Au(111) at fixed temperature, demonstrating a practical and direct method for controlling and potentially patterning FePc layers. Using scanning tunneling microscopy, we show that the diffusivity of FePc on Au(111) is a strong function of temperature and that applied electric fields can be used to retard or enhance molecular diffusion at fixed temperature. Using spin-dependent density-functional calculations, we then explore the origin of this effect, showing that applied fields modify both the molecule-surface binding energies and the molecular diffusion barriers through an interaction with the dipolar Fe-Au adsorption bond. On the basis of these results FePc on Au(111) is a promising candidate system for the development of adaptive molecular device structures.
Article
Gears are microfabricated down to diameters of a few micrometres. Natural macromolecular motors, of tens of nanometres in diameter, also show gear effects. At a smaller scale, the random rotation of a single-molecule rotor encaged in a molecular stator has been observed, demonstrating that a single molecule can be rotated with the tip of a scanning tunnelling microscope (STM). A self-assembled rack-and-pinion molecular machine where the STM tip apex is the rotation axis of the pinion was also tested. Here, we present the mechanics of an intentionally constructed molecule-gear on a Au(111) surface, mounting and centring one hexa-t-butyl-pyrimidopentaphenylbenzene molecule on one atom axis. The combination of molecular design, molecular manipulation and surface atomic structure selection leads to the construction of a fundamental component of a planar single-molecule mechanical machine. The rotation of our molecule-gear is step-by-step and totally under control, demonstrating nine stable stations in both directions.
Article
Molecular switches occur throughout nature. In one prominent example, light induces the isomerization of retinal from the compact 11-cis form to the elongated all-trans form, a conversion that triggers the transformation of light into a neural impulse in the eye. Applying these natural principles to synthetic systems offers a promising way to construct smaller and faster nanoelectronic devices. In such systems, electronic switches are essential components for storage and logical operations. The development of molecular switches on the single-molecule level would represent a major step toward Incorporating molecules as building units into nanoelectronic circuits. Molecular switches must be both reversible and bistable. To meet these requirements, a molecule must have at least two different thermally stable forms and a way to repeatedly inter-convert between those forms based on changes in light, heat, pressure, magnetic or electric fields, pH, mechanical forces, or electric currents. The conversion should be connected to a measurable change in electronic, optical, magnetic, or mechanical properties. Because isomers can differ significantly in physical and chemical properties, isomerization could serve as a molecular switching mechanism. Integration of molecular switches into larger circuits will probably require arranging them on surfaces, which will require a better understanding of isomerization reactions In these environments, In this Account, we describe our scanning tunneling microscopy studies of the isomerization of Individual molecules adsorbed on metal surfaces, Investigating chlorobenzene and azobenzene derivatives on the fcc(111) faces of Ag, Cu, and Au, we explored the influence of substituents and the substrate on the excitation mechanism of the Isomerization reaction induced by inelastically tunneling electrons. We achieved an irreversible configurational (cis-trans) isomerization of individual 4-dimethyl-amino-azobenzene-4-sulfonic add molecules on Au(111), a reversible configurational (cis-trans) isomerization of amino-nitro-azobenzene on Au(111), a constitutional (meta-ortho) Isomerization of chloronitrobenzene molecules adsorbed on Cu(111) and Au(111), and a constitutional (meta-para) isomerization of dichlorobenzene molecules adsorbed on Cu(111) and Ag(111). These studies demonstrate that we can Induce a variety of isomerization reactions by electron excitation on a metal surface. Our model isomerization studies provide a way to manipulate properties of single molecules, changing both their geometric structure and their physicochemical properties. The control of Isomerization of single molecules will advance the development of single-molecule electronics and other nanoscale processes.
Article
The ability of the scanning tunnelling microscope to manipulate single atoms and molecules has allowed a single bit of information to be represented by a single atom or molecule. Although such information densities remain far beyond the reach of real-world devices, it has been assumed that the finite spacing between atoms in condensed-matter systems sets a rigid upper limit on information density. Here, we show that it is possible to exceed this limit with a holographic method that is based on electron wavefunctions rather than free-space optical waves. Scanning tunnelling microscopy and holograms comprised of individually manipulated molecules are used to create and detect electronically projected objects with features as small as approximately 0.3 nm, and to achieve information densities in excess of 20 bits nm-2. Our electronic quantum encoding scheme involves placing tens of bits of information into a single fermionic state.
Article
The bonding of single diferrocene [Fc(CH(2))(14)Fc, Fc = ferrocenyl] molecules on a metal surface can be enhanced by partial decomposition of Fc groups induced by the tunneling current in scanning tunneling microscopy. Although the isolated intact molecule is mobile on the terrace of Cu(110) at 78 K, the modified molecule is immobilized on the terrace. Calculations based on density functional theory indicate that the hollow site of the Cu(110) surface is the energetically favorable adsorption site for both ferrocene and the Fe-cyclopentadienyl complex, but the latter one possesses a much higher binding energy with the substrate.