Stiffness calibration of qPlus sensors at low temperature through thermal noise measurements.

Non-contact atomic force microscopy (nc-AFM) offers a unique experimental framework for topographical imaging of surfaces with atomic and/or sub-molecular resolution. The technique also permits to perform frequency shift spectroscopy to quantitatively evaluate the tip-sample interaction forces and potentials above individual atoms or molecules. The stiffness of the probe, k, is then required to perform the frequency shift-to-force conversion. However, this quantity is generally known with little precision. An accurate stiffness calibration is therefore mandatory if accurate force measurements are targeted. In nc-AFM, the probe may either be a silicon cantilever, a quartz tuning fork (QTF), or a length extensional resonator (LER). When used in ultrahigh vacuum (UHV) and at low temperature, the technique mostly employs QTFs, based on the so-called qPlus design, which actually covers different types of sensors in terms of size and design of the electrodes. They all have in common a QTF featuring a metallic tip glued at the free end of one of its prongs. In this study, we report the stiffness calibration of a particular type of qPlus sensor in UHV and at 9.8 K by means of thermal noise measurements. The stiffness calibration of such high-k sensors, featuring high quality factors (Q) as well, requires to master both the acquisition parameters and the data post-processing. Our approach relies both on numerical simulations and experimental results. A thorough analysis of the thermal noise power spectral density of the qPlus fluctuations leads to an estimated stiffness of the first flexural eigenmode of ≃2000 N/m, with a maximum uncertainty of 10%, whereas the static stiffness of the sensor without tip is expected to be ≃3300 N/m. The former value must not be considered as being representative of a generic value for any qPlus, as our study stresses the influence of the tip on the estimated stiffness and points towards the need for the individual calibration of these probes. Although the framework focuses on a particular kind of sensor, it may be adapted to any high-k, high-Q nc-AFM probe used under similar conditions, such as silicon cantilevers and LERs.

Micrometre-long covalent organic fibres by photoinitiated chain-growth radical polymerization on an alkali-halide surface.

On-surface polymerization is a promising technique to prepare organic functional nanomaterials that are challenging to synthesize in solution, but it is typically used on metal substrates, which play a catalytic role. Previous examples on insulating surfaces have involved intermediate self-assembled structures, which face high barriers to diffusion, or annealing to higher temperatures, which generally causes rapid dewetting and desorption of the monomers. Here we report the photoinitiated radical polymerization, initiated from a two-dimensional gas phase, of a dimaleimide monomer on an insulating KCl surface. Polymer fibres up to 1 µm long are formed through chain-like rather than step-like growth. Interactions between potassium cations and the dimaleimide's oxygen atoms facilitate the propagation of the polymer fibres along a preferred axis of the substrate over long distances. Density functional theory calculations, non-contact atomic force microscopy imaging and manipulations at room temperature were used to explore the initiation and propagation processes, as well as the structure and stability of the resulting one-dimensional polymer fibres.

Dipole-driven self-organization of zwitterionic molecules on alkali halide surfaces.

We investigated the adsorption of 4-methoxy-4'-(3-sulfonatopropyl)stilbazolium (MSPS) on different ionic (001) crystal surfaces by means of noncontact atomic force microscopy. MSPS is a zwitterionic molecule with a strong electric dipole moment. When deposited onto the substrates at room temperature, MSPS diffuses to step edges and defect sites and forms disordered assemblies of molecules. Subsequent annealing induces two different processes: First, at high coverage, the molecules assemble into a well-organized quadratic lattice, which is perfectly aligned with the <110> directions of the substrate surface (i.e., rows of equal charges) and which produces a Moiré pattern due to coincidences with the substrate lattice constant. Second, at low coverage, we observe step edges decorated with MSPS molecules that run along the <110> direction. These polar steps most probably minimize the surface energy as they counterbalance the molecular dipole by presenting oppositely charged ions on the rearranged step edge.

Graphite, graphene on SiC, and graphene nanoribbons: Calculated images with a numerical FM-AFM.

BACKGROUND: Characterization at the atomic scale is becoming an achievable task for FM-AFM users equipped, for example, with a qPlus sensor. Nevertheless, calculations are necessary to fully interpret experimental images in some specific cases. In this context, we developed a numerical AFM (n-AFM) able to be used in different modes and under different usage conditions. RESULTS: Here, we tackled FM-AFM image calculations of three types of graphitic structures, namely a graphite surface, a graphene sheet on a silicon carbide substrate with a Si-terminated surface, and finally, a graphene nanoribbon. We compared static structures, meaning that all the tip and sample atoms are kept frozen in their equilibrium position, with dynamic systems, obtained with a molecular dynamics module allowing all the atoms to move freely during the probe oscillations. CONCLUSION: We found a very good agreement with experimental graphite and graphene images. The imaging process for the deposited nanoribbon demonstrates the stability of our n-AFM to image a non-perfectly planar substrate exhibiting a geometrical step as well as a material step.

Understanding the atomic-scale contrast in Kelvin probe force microscopy.

A numerical analysis of the origin of the atomic-scale contrast in Kelvin probe force microscopy is presented. Atomistic simulations of the tip-sample interaction force field have been combined with a noncontact atomic force microscope simulator including a Kelvin module. The implementation mimics recent experimental results on the (001) surface of a bulk alkali halide crystal for which simultaneous atomic-scale topographical and contact potential difference contrasts were reported. The local contact potential difference does reflect the periodicity of the ionic crystal, but not the magnitude of its Madelung surface potential. The imaging mechanism relies on the induced polarization of the ions at the tip-surface interface owing to the modulation of the applied bias voltage. Our findings are in excellent agreement with previous theoretical expectations and experimental observations.

On the relevance of the atomic-scale contact potential difference by amplitude-modulation and frequency-modulation Kelvin probe force microscopy.

The influence of short-range electrostatic forces on the measured local contact potential difference (CPD) by means of amplitude-modulation and frequency-modulation Kelvin probe force microscopy (AM- and FM-KPFM) is discussed on the base of numerical and analytical descriptions of both methods. The goal of this work is to help in interpreting recent experimental results reporting atomically resolved CPD images, in particular on bulk insulating samples. The discussion is carried out on the basis of spectroscopic curves. The expression of the bias-dependent electrostatic force is derived from a previous work and is estimated between a tip with simple geometry and the (001) facet of a perfect alkali halide single crystal. The force, with a short-range character, scales as a second-order polynomial function of the bias voltage. It is stated that the linear term is responsible for the occurrence of the atomic-scale CPD contrast, while the quadratic one, involving the sample polarization, accounts for the detected signal by the KPFM methods. Nevertheless, analytical and numerical approaches stress the influence of the linear term on the measured CPD which intrinsically hinders the possibility to perform quantitative CPD measurements, but also makes the measured 'pseudo-CPD' strongly deviating from the surface potential. Hence, in the short-range regime, AM- or FM-KPFM measurements neither reflect the CPD nor the local surface potential, but rather an effective value which is convoluted by the geometric parameters of the tip, the so-called local CPD. It is also stated that the local CPD measured by means of AM- or FM-KPFM differs when sub-nanometer vibration amplitudes of the cantilever are used. Otherwise, AM- and FM-KPFM measurements should be almost similar. At last, the influence of long-range, capacitive, electrostatic forces is discussed in conjunction with the short-range ones. This allows us to draw conclusions regarding the distance dependence of the local CPD which then exhibits a resonant behavior as a function of the tip-surface separation. This phenomenon is expected to play a role in the KPFM imaging process.

Robust supramolecular network on Ag(111): hydrogen-bond enhancement through partial alcohol dehydrogenation.

Alcohol oxidation and self-assembly: the in situ oxidation of hydroxyl functional groups to quinone groups promotes the formation of enhanced hydrogen bonds and allows reorganization of the resulting supramolecular self-assemblies, which evolve from a weakly bound dense phase to a strongly bound nanoporous open structure (see picture).