Adam Sweetman

Mapping the force field of a hydrogen-bonded assembly

Hydrogen bonding underpins the properties of a vast array of systems spanning a wide variety of scientific fields. From the elegance of base pair interactions in DNA to the symmetry of extended supramolecular assemblies, hydrogen bonds play an essential role in directing intermolecular forces. Yet fundamental aspects of the hydrogen bond continue to be vigorously debated. Here we use dynamic force microscopy (DFM) to quantitatively map the tip-sample force field for naphthalene tetracarboxylic diimide molecules hydrogen-bonded in two-dimensional assemblies. A comparison of experimental images and force spectra with their simulated counterparts shows that intermolecular contrast arises from repulsive tip-sample interactions whose interpretation can be aided via an examination of charge density depletion across the molecular system. Interpreting DFM images of hydrogen-bonded systems therefore necessitates detailed consideration of the coupled tip-molecule system: analyses based on intermolecular charge density in the absence of the tip fail to capture the essential physical chemistry underpinning the imaging mechanism.

Critical assessment of the evidence for striped nanoparticles

There is now a significant body of literature which reports that stripes form in the ligand shell of suitably functionalised Au nanoparticles. This stripe morphology has been proposed to strongly affect the physicochemical and biochemical properties of the particles. We critique the published evidence for striped nanoparticles in detail, with a particular focus on the interpretation of scanning tunnelling microscopy (STM) data (as this is the only technique which ostensibly provides direct evidence for the presence of stripes). Through a combination of an exhaustive re-analysis of the original data, in addition to new experimental measurements of a simple control sample comprising entirely unfunctionalised particles, we show that all of the STM evidence for striped nanoparticles published to date can instead be explained by a combination of well-known instrumental artefacts, or by issues with data acquisition/analysis protocols. We also critically re-examine the evidence for the presence of ligand stripes which has been claimed to have been found from transmission electron microscopy, nuclear magnetic resonance spectroscopy, small angle neutron scattering experiments, and computer simulations. Although these data can indeed be interpreted in terms of stripe formation, we show that the reported results can alternatively be explained as arising from a combination of instrumental artefacts and inadequate data analysis techniques.

Identifying passivated dynamic force microscopy tips on H:Si(100)

The chemical reactivity of the tip plays a central role in image formation in dynamic force microscopy, but in very many cases the state of the probe is a key experimental unknown. We show here that an H-terminated and thus chemically unreactive tip can be readily identified via characteristic imaging and spectroscopic (F(z)) signatures, including, in particular, contrast inversion, on hydrogen-passivated Si(100). We determine the tip apex termination by comparing site-specific difference force curves with the results of density functional theory, providing a clear protocol for the identification of chemically unreactive tips on silicon surfaces.

Effect of the tip state during qPlus noncontact atomic force microscopy of Si(100) at 5 K: Probing the probe

Summary Background: Noncontact atomic force microscopy (NC-AFM) now regularly produces atomic-resolution images on a wide range of surfaces, and has demonstrated the capability for atomic manipulation solely using chemical forces. Nonetheless, the role of the tip apex in both imaging and manipulation remains poorly understood and is an active area of research both experimentally and theoretically. Recent work employing specially functionalised tips has provided additional impetus to elucidating the role of the tip apex in the observed contrast. Results: We present an analysis of the influence of the tip apex during imaging of the Si(100) substrate in ultra-high vacuum (UHV) at 5 K using a qPlus sensor for noncontact atomic force microscopy (NC-AFM). Data demonstrating stable imaging with a range of tip apexes, each with a characteristic imaging signature, have been acquired. By imaging at close to zero applied bias we eliminate the influence of tunnel current on the force between tip and surface, and also the tunnel-current-induced excitation of silicon dimers, which is a key issue in scanning probe studies of Si(100). Conclusion: A wide range of novel imaging mechanisms are demonstrated on the Si(100) surface, which can only be explained by variations in the precise structural configuration at the apex of the tip. Such images provide a valuable resource for theoreticians working on the development of realistic tip structures for NC-AFM simulations. Force spectroscopy measurements show that the tip termination critically affects both the short-range force and dissipated energy.

Uncertainties in forces extracted from non-contact atomic force microscopy measurements by fitting of long-range background forces

Summary In principle, non-contact atomic force microscopy (NC-AFM) now readily allows for the measurement of forces with sub-nanonewton precision on the atomic scale. In practice, however, the extraction of the often desired ‘short-range’ force from the experimental observable (frequency shift) is often far from trivial. In most cases there is a significant contribution to the total tip–sample force due to non-site-specific van der Waals and electrostatic forces. Typically, the contribution from these forces must be removed before the results of the experiment can be successfully interpreted, often by comparison to density functional theory calculations. In this paper we compare the ‘on-minus-off’ method for extracting site-specific forces to a commonly used extrapolation method modelling the long-range forces using a simple power law. By examining the behaviour of the fitting method in the case of two radically different interaction potentials we show that significant uncertainties in the final extracted forces may result from use of the extrapolation method.

Imaging and manipulation of the Si(100) surface by small-amplitude NC-AFM at zero and very low applied bias

We use a noncontact atomic force microscope in the qPlus configuration to investigate the structure and influence of defects on the Si(100) surface. By applying millivolt biases, simultaneous tunnel current data is acquired, providing information about the electronic properties of the surface at biases often inaccessible during conventional STM imaging, and highlighting the difference between the contrast observed in NC-AFM and tunnel current images. We also show how NC-AFM (in the absence of tunnel current) can be used to manipulate both the clean c(4 × 2) surface and dopant-related defects.

qPlus atomic force microscopy of the Si(100) surface: Buckled, split-off, and added dimers

Dimer configurations at the Si(100) surface have been studied with noncontact atomic force microscopy in the qPlus mode at 77 K, using both large (10 nm peak to peak) and small (0.5 nm peak to peak) oscillation amplitudes. In addition to the p(2×1), p(2×2), and c(4×2) reconstructions of the pristine surface, a variety of defect types including ad-dimers, vacancies, and split-off dimers have been imaged. Our data appear at odds with the currently accepted structural model for split-off dimers. At low oscillation amplitudes the degree of apparent dimer buckling can be “tuned” by varying the frequency shift set point.

Measuring Si-C60 chemical forces via single molecule spectroscopy

We measure the short-range chemical force between a silicon-terminated tip and individual adsorbed C(60) molecules using frequency modulation atomic force microscopy. The interaction with an adsorbed fullerene is sufficiently strong to drive significant atomic rearrangement of tip structures.

Visualizing the orientational dependence of an intermolecular potential

Scanning probe microscopy can now be used to map the properties of single molecules with intramolecular precision by functionalization of the apex of the scanning probe tip with a single atom or molecule. Here we report on the mapping of the three-dimensional potential between fullerene (C60) molecules in different relative orientations, with sub-Angstrom resolution, using dynamic force microscopy (DFM). We introduce a visualization method which is capable of directly imaging the variation in equilibrium binding energy of different molecular orientations. We model the interaction using both a simple approach based around analytical Lennard–Jones potentials, and with dispersion-force-corrected density functional theory (DFT), and show that the positional variation in the binding energy between the molecules is dominated by the onset of repulsive interactions. Our modelling suggests that variations in the dispersion interaction are masked by repulsive interactions even at displacements significantly larger than the equilibrium intermolecular separation.

Mechano-chemical manipulation of Sn chains on Si(1 0 0) by NC-AFM

We investigate the atomic structure of Sn dimer chains grown on the Si(1 0 0) surface using non-contact atomic force microscopy (NC-AFM) at cryogenic temperatures. We find that similar to the native Si(1 0 0) dimer structure, the ground state of the Sn dimer structure is buckled at low temperature. At 5 K we show that the buckling state of the Sn dimers may be controllably, and reversibly, manipulated with atomic precision by close approach of the tip, without modification of the underlying substrate buckling structure. At intermediate cryogenic temperatures we observe changes in the configuration of the dimer chains in the region where the tip-sample interaction is very weak, suggesting that the energy barrier to transit between configurations is sufficiently small to be surmounted at 78 K.