RESUMEN
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.
RESUMEN
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.
RESUMEN
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.