Tip-sample Interaction Research Articles

Coarse-Grained MD Simulations of the Capillary Interaction between a Sphere and a Binary Fluid with Truncated Lennard-Jones Potentials.

In atomic force microscopy experiments on fluid samples, a capillary bridge forms between the tip and the fluid, causing an attractive capillary force. Here, we present a computational model of the capillary interaction between a solid sphere and a coarse-grained Lennard-Jones fluid containing 10% antifreeze particles with an enlarged van der Waals radius. The capillary force acting on the sphere is obtained from the displacement of the sphere in a trap potential as the sphere is incrementally approached and then retracted from the fluid. This yields force-distance data similar to that obtained in atomic force microscopy experiments. We use this methodology to study the influence of the cutoff radius of the truncated Lennard-Jones potentials on the capillary force and its temperature dependence. The latter is found to scale with the critical temperature of the system. With the presented approach, the tip-sample interaction can be studied for a wide range of complex fluids, particle shapes, and force-probing schemes.

Focused electron beam induced deposition of magnetic tips for improved magnetic force microscopy

The combination of focused electron beam induced deposition (FEBID) and magnetic force microscopy (MFM) has opened up new possibilities in nanoscale magnetic imaging. FEBID offers precise control over the dimensions and magnetic properties of the MFM probes, enabling the development of high-performance magnetic tips with enhanced capabilities compared to conventional ones. These improved tips offer superior resolution, sensitivity, and versatility in nanoscale magnetic surface characterization. Here, we compare the performance of a commercial MFM tip and a FEBID-grown Fe tip in a Ni80Fe20/NdCo5 film. The FEBID tip exhibited superior lateral resolution for topography imaging, likely due to its sharper and well-defined geometry, with a tip diameter of approximately 20 nm. MFM measurements further confirmed this advantage, revealing better-defined magnetic domains and higher magnetic contrast with the FEBID-functionalized probes compared to the commercial tip. This improvement can be attributed to the possibility to optimize the tip-sample magnetic interaction for the FEBID tip. By reducing the lift height of the second pass, we were able to bring the tip closer to the sample, enhancing the magnetic signal without introducing significant topographic artifacts. Overall, these findings highlight the potential of FEBID for creating high-resolution and high-sensitivity MFM tips.

Novel hybrid interference and atomic force microscopy

Abstract A novel hybrid microscope which combines an interference microscopic (IM) and an atomic force microscopic (AFM) measurement mode is introduced. It is realised by adding an AFM probe to an IM, where the AFM probe can be mechanically switched in or out of the beam path of the IM. When the AFM cantilever is out of the beam path, the system works in the IM measurement mode for noncontact and fast optical measurements. When the AFM cantilever is in the beam path, it works in the AFM measurement mode, where the AFM tip interacts with sample surfaces for measurements. The deformation of the AFM cantilever induced by the tip-sample interaction force is detected from interference fringes, which are formed by the interference of the light beam reflected from the backside of the AFM cantilever and a reference beam in the IM. This novel design has a high-level synergy of AFM and IM technologies and provides several promising application potentials. For instance, it can bring high-resolution AFM measurements whenever and wherever needed in IM measurements, thus, to complement the lateral resolution limits of IM; The AFM measurement mode can provide measurement results with higher topography fidelity, thus, to offer in-situ reference areal surface metrology for IM measurements. In the paper, design concept, realisation of a prototype instrument, and experimental results illustrating the performance of the prototype instrument are detailed. 

Characterization of strongly coupled quartz tuning fork sensors for precision force measurement in atomic force microscopy

Miniaturized quartz tuning forks (QTFs) have been adopted as force sensors for non-contact atomic force microscopy (AFM). However, the coupled oscillation behaviors of the QTF prongs are not well understood, preventing quantitative measurement of the nanoscale tip-sample interaction forces. This article presents a lumped model that accurately delineates the coupled mechanical oscillations of QTF prongs, establishing rigorous relationships between experimental observables and tip-sample interaction forces. The first-order resonance spectra of a commercial QTF were fully characterized by correlating its piezoelectric response with the actual mechanical oscillation measured with a Fabry-Pérot interferometer. In order to uniquely determine the modeling parameters (i.e., the effective masses, spring constants, and damping constants), the experimental results were compared with the lumped model predictions while masses were added to one prong. The results reveal that the QTF’s center of mass is highly damped, preventing the observation of a symmetric resonance mode. In addition, the mass loading experiment demonstrates that the mechanical oscillations of the QTF prongs are strongly coupled, accounting for 59% (84%) of the effective stiffness at the in-plane (out-of-plane), antisymmetric resonance mode. We believe that the obtained QTF characterization results will pave the way for quantitative measurements of non-contact interaction forces in QTF-based AFM platforms, significantly improving the precision and reliability of nanoscale force measurements.

Heterodyne High-Harmonic Electrostatic Force Microscopy with Improved Spatial Resolution for Nanoscale Identification of Metallic/Semiconducting Carbon Nanotubes.

There are two main types of carbon nanotubes (CNTs): metallic and semiconducting. Naturally grown CNTs are randomly distributed, posing challenges in distinguishing between the two types. Here, a novel approach for nanoscale high-resolution imaging and identification of CNTs was introduced by incorporating the heterodyne technique into high-harmonic electrostatic force microscopy (HH-EFM) on an atomic force microscopy (AFM) platform. In the developed heterodyne HH-EFM, a more localized high-order gradient of tip-sample nonlinear interaction force is used as signal channels, resulting in an improved spatial resolution, compared to the conventional HH-EFM. Furthermore, the heterodyne HH-EFM also has the capability to visualize material carrier density and assess qualitative carrier transport performance. Our work not only presents a new approach to identifying/exploring electrical properties of low-dimensional nanomaterials but also provides a solution for optimizing resolution in long-range interaction-based functional AFM technologies.

Local probing of the nanoscale hydration landscape of kaolinite basal facets in the presence of ions

The interface between aqueous solutions and the facets of kaolinite plays an important role in a wide range of technological applications including tribology, paper production, oil recovery, waste water treatment and medical devices. This is made possible by kaolinite's layered structure, with its two basal surfaces -aluminol and siloxane-exhibiting different properties and reactivity. Using a combination of high-resolution atomic force microscopy (AFM) and atomistic molecular dynamics (MD) simulations, we probe in situ the hydration structure over both facets, in water and in the presence of added NaCl. The AFM images reflect the facets' first hydration layer, as confirmed from simulations. Complementary AFM spectroscopy measurements show an excellent agreement between the conservative component and MD's water density profiles, with discrete hydration layers on both facets and little sensitivity to added ions. The dissipative component of the measured tip-sample interactions is more sensitive to the presence of ions, with MD suggesting a link with the local water dynamics and transient instabilities between stable hydration layers. These effects are facet-dependant and more pronounced on the aluminol facet where the first water layer is better defined. Increasing the salt concentration allows hydrated ions to form more stable layers, with hints of organised ionic domains. The results provide unique insights into both the equilibrium molecular structure and dynamics of the kaolinite facets, potentially informing applications involving interfacial processes.

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.

Thermal noise calibration of functionalized cantilevers for force microscopy: Effects of the colloidal probe position

Colloidal probes are often used in force microscopy when the geometry of the tip–sample interaction should be well controlled. Their calibration requires an understanding of their mechanical response, which is very sensitive to the details of the force sensor consisting of a cantilever and the attached colloid. We present some analytical models to describe the dynamics of the cantilever and its load positioned anywhere along its length. The thermal noise calibration of such probes is then studied from a practical point of view, leading to correction coefficients that can be applied in standard force microscope calibration routines. Experimental measurements of resonance frequencies and thermal noise profiles of raw and loaded cantilevers demonstrate the validity of the approach.

Enhanced feedback performance in off-resonance AFM modes through pulse train sampling.

Dynamic atomic force microscopy (AFM) modes that operate at frequencies far away from the resonance frequency of the cantilever (off-resonance tapping (ORT) modes) can provide high-resolution imaging of a wide range of sample types, including biological samples, soft polymers, and hard materials. These modes offer precise and stable control of vertical force, as well as reduced lateral force. Simultaneously, they enable mechanical property mapping of the sample. However, ORT modes have an intrinsic drawback: a low scan speed due to the limited ORT rate, generally in the low-kilohertz range. Here, we analyze how the conventional ORT control method limits the topography tracking quality and hence the imaging speed. The closed-loop controller in conventional ORT restricts the sampling rate to the ORT rate and introduces a large closed-loop delay. We present an alternative ORT control method in which the closed-loop controller samples and tracks the vertical force changes during a defined time window of the tip-sample interaction. Through this, we use multiple samples in the proximity of the maximum force for the feedback loop, rather than only one sample at the maximum force instant. This method leads to improved topography tracking at a given ORT rate and therefore enables higher scan rates while refining the mechanical property mapping.

How Precisely Can Individual Molecules Be Analyzed? A Case Study on Locally Quantifying Forces and Energies Using Scanning Probe Microscopy.

Recent advances in scanning probe microscopy methodology have enabled the measurement of tip-sample interactions with picometer accuracy in all three spatial dimensions, thereby providing a detailed site-specific and distance-dependent picture of the related properties. This paper explores the degree of detail and accuracy that can be achieved in locally quantifying probe-molecule interaction forces and energies for adsorbed molecules. Toward this end, cobalt phthalocyanine (CoPc), a promising CO2 reduction catalyst, was studied on Ag(111) as a model system using low-temperature, ultrahigh vacuum noncontact atomic force microscopy. Data were recorded as a function of distance from the surface, from which detailed three-dimensional maps of the molecule's interaction with the tip for normal and lateral forces as well as the tip-molecule interaction potential were constructed. The data were collected with a CO molecule at the tip apex, which enabled a detailed visualization of the atomic structure. Determination of the tip-substrate interaction as a function of distance allowed isolation of the molecule-tip interactions; when analyzing these in terms of a Lennard-Jones-type potential, the atomically resolved equilibrium interaction energies between the CO tethered to the tip and the CoPc molecule could be recovered. Interaction energies peaked at less than 160 meV, indicating a physisorption interaction. As expected, the interaction was weakest at the aromatic hydrogens around the periphery of the molecule and strongest surrounding the metal center. The interaction, however, did not peak directly above the Co atom but rather in pockets surrounding it.

Calibration of the oscillation amplitude of quartz tuning fork-based force sensors with astigmatic displacement microscopy.

Quartz tuning forks and qPlus-based force sensors offer an alternative approach to silicon cantilevers for investigating tip-sample interactions in scanning probe microscopy. The high-quality factor (Q) and stiffness of these sensors prevent the tip from jumping to the contact, even at sub-nanometer amplitude. The qPlus configuration enables simultaneous scanning tunneling microscopy and atomic force microscopy, achieving spatial resolution and spectroscopy at the subatomic level. However, to enable precise measurement of tip-sample interaction forces, confidence in these measurements is contingent upon the accurate calibration of the spring constant and oscillation amplitude of the sensor. Here, we have developed a method called astigmatic displacement microscopy with picometer sensitivity.

Reconstruction of shear force in Atomic Force Microscopy from measured displacement of the cone-shaped cantilever tip

<abstract><p>We present a new comprehensive mathematical model of the cone-shaped cantilever tip-sample interaction in Atomic Force Microscopy (AFM). The importance of such AFMs with cone-shaped cantilevers can be appreciated when its ability to provide high-resolution information at the nanoscale is recalled. It is an indispensable tool in a wide range of scientific and industrial fields. The interaction of the cone-shaped cantilever tip with the surface of the specimen (sample) is modeled by the damped Euler-Bernoulli beam equation $ \rho_A(x)u_{tt} $ $ +\mu(x)u_{t}+(r(x)u_{xx}+\kappa(x)u_{xxt})_{xx} = 0 $, $ (x, t)\in (0, \ell)\times (0, T) $, subject to the following initial, $ u(x, 0) = 0 $, $ u_t(x, 0) = 0 $ and boundary, $ u(0, t) = 0 $, $ u_{x}(0, t) = 0 $, $ \left (r(x)u_{xx}(x, t)+\kappa(x)u_{xxt} \right)_{x = \ell} = M(t) $, $ \left (-(r(x)u_{xx}+\kappa(x)u_{xxt})_x\right)_{x = \ell} = g(t) $ conditions, where $ M(t): = 2h\cos \theta\, g(t)/\pi $ is the moment generated by the transverse shear force $ g(t) $. Based on this model, we propose an inversion algorithm for the reconstruction of an unknown shear force in the AFM cantilever. The measured displacement $ \nu(t): = u(\ell, t) $ is used as additional data for the reconstruction of the shear force $ g(t) $. The least square functional $ J(F) = \frac{1}{2}\Vert u(\ell, \cdot)-\nu \Vert_{L^2(0, T)}^2 $ is introduced and an explicit gradient formula for the Fréchet derivative of the cost functional is derived via the weak solution of the adjoint problem. Additionally, the geometric parameters of the cone-shaped tip are explicitly contained in this formula. This enables us to construct a gradient based numerical algorithm for the reconstructions of the shear force from noise free as well as from random noisy measured output $ \nu (t) $. Computational experiments show that the proposed algorithm is very fast and robust. This creates the basis for developing a numerical "gadget" for computational experiments with generic AFMs.</p></abstract>

Research on AFM tip-related nanofabrication of two-dimensional materials

Abstract With the great success of graphene, two-dimensional (2D) materials, thanks to their fascinating electronic and optoelectronic properties, have aroused extensive attention among the scientific community. Broad research efforts have proven the enormous potential of 2D materials in optoelectronics, electrochemistry, spintronics, energy storage, catalysis, biomedicine, and many other fields. Driven by the promising applications of 2D materials, there has been an emerging trend toward nanofabricating 2D materials with customized parameters, which are essential for tailor-making controllable artificial nanostructures used in building sophisticated 2D material systems. As the most commonly used solid probe lithography technique, atomic force microscopy (AFM) integrates visualization and multi-mode fabrication within one system, demonstrating its superior capability in the nanofabrication of 2D materials. In view of this, in this review article, we offer a brief introduction to how AFM nanofabrication works and the classification of AFM nanofabrication techniques by the tip-sample surface interaction. Following that, we discuss the results of 2D material nanofabrication by mechanical, thermal, electrical, and other AFM techniques in which external stimulations are applied on special AFM probes.

Remote-Controllable Interfacial Electron Tunneling at Heterogeneous Molecular Junctions via Tip-Induced Optoelectrical Engineering.

Molecular electronics enables functional electronic behavior via single molecules or molecular self-assembled monolayers, providing versatile opportunities for hybrid molecular-scale electronic devices. Although various molecular junction structures are constructed to investigate charge transfer dynamics, significant challenges remain in terms of interfacial charging effects and far-field background signals, which dominantly block the optoelectrical observation of interfacial charge transfer dynamics. Here, tip-induced optoelectrical engineering is presented that synergistically correlates photo-induced force microscopy and Kelvin probe force microscopyto remotely control and probe the interfacial charge transfer dynamics with sub-10nm spatial resolution. Based on this approach, the optoelectrical origin of metal-molecule interfaces is clearly revealed by the nanoscale heterogeneity of the tip-sample interaction and optoelectrical reactivity, which theoretically aligned with density functional theory calculations. For a practical device-scale demonstration of tip-induced optoelectrical engineering, interfacial tunneling is remotely controlled at a 4-inch wafer-scale metal-insulator-metal capacitor, facilitating a 5.211-fold current amplification with the tip-induced electrical field. In conclusion, tip-induced optoelectrical engineering provides a novel strategy to comprehensively understand interfacial charge transfer dynamics and a non-destructive tunneling control platform that enables real-time and real-space investigation of ultrathin hybrid molecular systems.

Three-dimensional photoinduced force microscopy reveals artifacts from photothermal tip vibrations

Photoinduced force microscopy (PiFM) is a technique for nanoscale characterization of optically active materials. For correct data analysis, it is important to understand and recognize potential artifacts. In this study, we provide a Fourier-based framework for the different origins of the photoinduced force, including the photothermal motion of the atomic force microscopy (AFM) tip in PiFM measurements. We use individual gold nanoparticles as a model system to explore such tip-related phenomena and to demonstrate the benefits of three-dimensional analysis of the photoinduced force. Comparison of the in-phase heterodyne PiFM signal and the derivative of the tip–sample interaction, ∂⟨kts⟩/∂zc, directly reveals a photothermal origin for the PiFM signal in our experiments. Furthermore, we observe a lateral photothermal vibration of the tip apex induced by tip asymmetry. This lateral vibration emphasizes the importance of considering the motion of the AFM tip during data analysis. The improved lateral resolution conferred by ∂⟨kts⟩/∂zc can lead to misinterpretation. Our findings highlight that meticulous data analysis is required to ensure the correct interpretation of PiFM data.

Simultaneous detection of force and tunneling current in electrolyte solution by using qPlus sensor.

We have developed a sensor for simultaneous measurement of atomic force microscopy (AFM) and scanning tunneling microscopy (STM) under liquid environments. The sensor, which is based on the qPlus sensor, is equipped with an insulated conductive tip. Owing to its electrical insulation except for the tip apex, the developed sensor enabled simultaneous detection of tip-sample interaction force and tunneling current, suppressing the Faradaic leakage current. As a fundamental demonstration, we performed simultaneous AFM/STM imaging in an electrolyte solution by using the developed sensor.

On the Nonlinear Stochastic Dynamics of an Atomic Force Microscope Cantilever

AbstractAtomic force microscopy (AFM) serves characterization and actuation in nanoscale applications. We study the stochastic dynamics of an AFM cantilever under tip-sample interactions represented by the Lennard–Jones and Morse potential energy functions. In both cases, we also study the contrasting dynamic effects of additive (external) and multiplicative (internal) noise. Moreover, for multiplicative noise, we study the two sub-cases arising from the Itô and Stratonovich interpretations of stochastic integrals. In each case, we also investigate the stochastic stability of the system by tracing the time evolution of the maximal Lyapunov exponent. Additionally, we obtain stationary probability densities for the unforced dynamics using stochastic averaging.

Customization of an atomic force microscope for multidimensional measurements under environmental conditions.

Atomic force microscopy (AFM) is an analytical surface characterization tool that reveals the surface topography at a nanometer length scale while probing local chemical, mechanical, and even electronic sample properties. Both contact (performed with a constant deflection of the cantilever probe) and dynamic operation modes (enabled by demodulation of the oscillation signal under tip-sample interaction) can be employed to conduct AFM-based measurements. Although surface topography is accessible regardless of the operation mode, the resolution and the availability of the quantified surface properties depend on the mode of operation. However, advanced imaging techniques, such as frequency modulation, to achieve high resolution, quantitative surface properties are not implemented in many commercial systems. Here, we show the step-by-step customization of an atomic force microscope. The original system was capable of surface topography and basic force spectroscopy measurements while employing environmental control, such as temperature variation of the sample/tip, etc. We upgraded this original setup with additional hardware (e.g., a lock-in amplifier with phase-locked loop capacity, a high-voltage amplifier, and a new controller) and software integration while utilizing its environmental control features. We show the capabilities of the customized system with frequency modulation-based topography experiments and automated voltage and/or distance spectroscopy, time-resolved AFM, and two-dimensional force spectroscopy measurements under ambient conditions. We also illustrate the enhanced stability of the setup with active topography and frequency drift corrections. We believe that our methodology can be useful for the customization and automation of other scanning probe systems.

High-speed multiparametric imaging through off-resonance tapping AFM with active probe

Off-resonance tapping (ORT) mode of atomic force microscopy (AFM), based on force-distance curve, is widely concerned due to its advantages of weak tip-sample interaction and concurrent quantitative property mapping. However, the ORT-AFM still has the disadvantage of slow scan speed caused by low modulation frequency. In this paper, we overcome this disadvantage by introducing active probe method. With active probe, the cantilever was directly actuated with the induced strain after applying voltage in the piezoceramic film. In this way, the modulation frequency could be increased to more than an order of magnitude faster than that of traditional ORT, thus improving the scan rate. We demonstrated high-speed multiparametric imaging with the active probe method in ORT-AFM.

Are High Resolution Atomic Force Microscopy images proportional to the force gradient or the force maps?

Frequency modulation Atomic Force Microscopy using tips functionalized with carbon monoxide (also known as High Resolution AFM) shows an extraordinary resolution on molecules and it can disclose their inner structure on the frequency shift maps. When operating the microscope at low amplitudes, <1 Å, these frequency shift measurements have been traditionally interpreted as the force gradient between the probe and the sample. Here, we show that, for CO-terminated tips, this interpretation fails even for amplitudes as small as 0.2–0.3 Å. The main reason behind this failure is the very rapid variation in tip-sample interaction upon tip approach associated with the mobility of the CO probe, which deflects to reduce the Pauli repulsion with the sample. Besides, we propose a new and very simple approach for the frequency shift in terms of the force at the closest tip-sample separation. This force approximation reproduces the real frequency maps for amplitudes larger than ∼0.3 Å, independent of CO deflection.