Oscar Custance

Chemical identification of individual surface atoms by atomic force microscopy

Scanning probe microscopy is a versatile and powerful method that uses sharp tips to image, measure and manipulate matter at surfaces with atomic resolution. At cryogenic temperatures, scanning probe microscopy can even provide electron tunnelling spectra that serve as fingerprints of the vibrational properties of adsorbed molecules and of the electronic properties of magnetic impurity atoms, thereby allowing chemical identification. But in many instances, and particularly for insulating systems, determining the exact chemical composition of surfaces or nanostructures remains a considerable challenge. In principle, dynamic force microscopy should make it possible to overcome this problem: it can image insulator, semiconductor and metal surfaces with true atomic resolution, by detecting and precisely measuring the short-range forces that arise with the onset of chemical bonding between the tip and surface atoms and that depend sensitively on the chemical identity of the atoms involved. Here we report precise measurements of such short-range chemical forces, and show that their dependence on the force microscope tip used can be overcome through a normalization procedure. This allows us to use the chemical force measurements as the basis for atomic recognition, even at room temperature. We illustrate the performance of this approach by imaging the surface of a particularly challenging alloy system and successfully identifying the three constituent atomic species silicon, tin and lead, even though these exhibit very similar chemical properties and identical surface position preferences that render any discrimination attempt based on topographic measurements impossible.

Complex Patterning by Vertical Interchange Atom Manipulation Using Atomic Force Microscopy

The ability to incorporate individual atoms in a surface following predetermined arrangements may bring future atom-based technological enterprises closer to reality. Here, we report the assembling of complex atomic patterns at room temperature by the vertical interchange of atoms between the tip apex of an atomic force microscope and a semiconductor surface. At variance with previous methods, these manipulations were produced by exploring the repulsive part of the short-range chemical interaction between the closest tip-surface atoms. By using first-principles calculations, we clarified the basic mechanisms behind the vertical interchange of atoms, characterizing the key atomistic processes involved and estimating the magnitude of the energy barriers between the relevant atomic configurations that leads to these manipulations.

Room-temperature reproducible spatial force spectroscopy using atom-tracking technique

A method for reproducible site-specific force spectroscopic measurements using frequency modulation atomic force microscopy at room temperature is presented. The stability and reproducibility requirements, fulfilled so far only in cryogenic environment, are provided through the compensation of the thermal drift using the atom-tracking technique. The method has been tested performing spectroscopic measurements on atomic positions of the Si(111)-(7×7) surface with Si tips. The room-temperature results presented here compare in quality to previously reported quantitative force spectroscopic data obtained at cryogenic temperatures.

Lateral manipulation of single atoms at semiconductor surfaces using atomic force microscopy

Experimental results on the lateral manipulation of single atoms at semiconductor surfaces using non-contact atomic force microscopy (NC-AFM) are presented. These experiments prove that deposited adsorbates on top of a surface, as well as intrinsic adatoms of semiconductor surfaces, are suitable for being manipulated using the short-range interaction force acting between the outermost atoms of a semiconductor tip and the atoms at the surface. The analysis of the data from some of the experiments presented here indicates a pulling process of the tip on the manipulated atoms. The atom-by-atom creation, at room temperature, of patterns composed by a few inherent atoms of a heterogeneous surface is also presented.

Atom tracking for reproducible force spectroscopy at room temperature with non-contact atomic force microscopy

A method for reproducible site-specific force spectroscopic measurements at room temperature by combining frequency modulation atomic force microscopy and the atom tracking technique is proposed. The atom tracking enables us to compensate the change in the tip–sample relative position induced by the thermal drift as well as to precisely position the tip over the same spot of the surface within sub-Angstrom stability. Here, we describe our atom-tracking implementation and the protocol we have followed for the reproducible room-temperature acquisition of series of frequency shift versus tip–sample distance (Δf–Z) curves using this technique. With this acquisition protocol, a large number of equivalent Δf–Z curves can be averaged, resulting in a considerable noise reduction, and therefore avoiding its propagation to the corresponding calculated force curve.

Dynamic force spectroscopy using cantilever higher flexural modes

By means of force spectroscopy measurements performed with the cantilever first and second flexural modes under the frequency modulation detection method, the authors corroborate the validity of the relation between tip-surface interaction force and frequency shift for force spectroscopy acquisition using higher cantilever eigenmodes. They estimate a cantilever effective stiffness for the second eigenmode 73 times larger than the static stiffness. This large effective stiffness enables them to perform force spectroscopy with a cantilever oscillation amplitude (A0) as small as 3.6A. The authors provide experimental evidence that, at such small A0 values, normalized frequency shift curves deviate from a A03∕2 scaling and the signal-to-noise ratio is considerably enhanced.

Imaging Three-Dimensional Surface Objects with Submolecular Resolution by Atomic Force Microscopy

Submolecular imaging by atomic force microscopy (AFM) has recently been established as a stunning technique to reveal the chemical structure of unknown molecules, to characterize intramolecular charge distributions and bond ordering, as well as to study chemical transformations and intermolecular interactions. So far, most of these feats were achieved on planar molecular systems because high-resolution imaging of three-dimensional (3D) surface structures with AFM remains challenging. Here we present a method for high-resolution imaging of nonplanar molecules and 3D surface systems using AFM with silicon cantilevers as force sensors. We demonstrate this method by resolving the step-edges of the (101) anatase surface at the atomic scale by simultaneously visualizing the structure of a pentacene molecule together with the atomic positions of the substrate and by resolving the contour and probe-surface force field on a C60 molecule with intramolecular resolution. The method reported here holds substantial promise for the study of 3D surface systems such as nanotubes, clusters, nanoparticles, polymers, and biomolecules using AFM with high resolution.

Atomic species identification at the (101) anatase surface by simultaneous scanning tunnelling and atomic force microscopy

Anatase is a pivotal material in devices for energy-harvesting applications and catalysis. Methods for the accurate characterization of this reducible oxide at the atomic scale are critical in the exploration of outstanding properties for technological developments. Here we combine atomic force microscopy (AFM) and scanning tunnelling microscopy (STM), supported by first-principles calculations, for the simultaneous imaging and unambiguous identification of atomic species at the (101) anatase surface. We demonstrate that dynamic AFM-STM operation allows atomic resolution imaging within the materials band gap. Based on key distinguishing features extracted from calculations and experiments, we identify candidates for the most common surface defects. Our results pave the way for the understanding of surface processes, like adsorption of metal dopants and photoactive molecules, that are fundamental for the catalytic and photovoltaic applications of anatase, and demonstrate the potential of dynamic AFM-STM for the characterization of wide band gap materials.

Manipulation of individual water molecules on CeO2(111)

Water molecules adsorbed on the CeO(2)(111) surface are investigated by non-contact atomic force microscopy (NC-AFM) at several tip-sample temperatures ranging between 10 and 300 K. Depending on the strength of the tip-surface interaction, they appear as triangular protrusions extended over three surface oxygen atoms or as small pits at hollow sites. During NC-AFM imaging with the tip being close to the surface, occasionally the transfer of molecules between tip and surface or the tip-induced lateral displacement of water molecules to equivalent surface lattice sites is observed. We report how this situation can be exploited to produce controlled lateral manipulations. A protocol to manipulate the water molecules between pre-defined neighbouring equivalent adsorption sites of the regular lattice as well as across a surface oxygen vacancy is demonstrated.

Force Spectroscopy on Semiconductor Surfaces

In this chapter, we introduce recent works on force spectroscopy performed using the frequency modulation detection method that have contributed to widen the knowledge and applicability of atomic force microscopy (AFM) for the study of surfaces with atomic resolution. We first introduce some experimental considerations regarding force spectroscopy acquisition. Then, we discuss how the combination force spectroscopy and first-principle calculations has contributed to clearly identify a channel for the dissipation of energy from the cantilever oscillation, as well as to clarify the interplay between atomic relaxations and differences in the tip–surface short-range interaction detected over atoms populating heterogeneous semiconductor surfaces. We introduce a protocol for single-atom chemical identification using AFM, which is based on the precise quantification of the tip–surface short-range interaction forces. Finally, anticipating the future general use of small cantilever oscillation amplitudes, we discuss force spectroscopy acquisition using higher flexural modes of rectangular cantilevers and oscillation amplitude values as small as 3.6 Ǻ.