Mode Atomic Force Microscopy Research Articles

Mechanisms of Multiple Functional Groups in Post-CMP Cleaning Solutions for Co Interconnects

Cobalt (Co) exhibits low resistivity, excellent adhesive properties, and the ability to fill gaps seamlessly, thus it is promising to change the landscape of integrated circuits in various fields, especially in the areas of interconnections and logic contacts. The cleaning of Co surfaces after chemical mechanical polishing (CMP) is an essential step due to the potential occurrence of numerous defects, such as silicon dioxide nanoparticles, organic residues, and severe corrosion. This research delves into the mechanisms of pivotal components in cleaning solutions, including complexing agents and corrosion inhibitors, and analyzes their impact on cleaning effectiveness. Based on Derjaguin-Landau-Verwey-Overbeek theory calculation and adhesion force measurements through the liquid mode of atomic force microscope, the interaction forces between silica (SiO2) particles and Co substrate were calculated and verified. Additionally, various methods were employed to unravel the nature of the particles and the mechanism of different functional groups, encompassing electrochemical experiments, static etching tests, surface energy studies, zeta potential measurements, and X-ray photoelectron spectroscopy characterization. This comprehensive investigation offers a clear understanding of the roles played by different functional groups, establishes a functional group system for cleaning solutions tailored to Co interconnect wafers, and provides valuable guidance for the subsequent design and development of cleaning solutions.

Schottky Diode Leakage Current Fluctuations: Electrostatically Induced Flexoelectricity in Silicon.

Nearly four decades have passed since IBM scientists pioneered atomic force microscopy (AFM) by merging the principles of a scanning tunneling microscope with the features of a stylus profilometer. Today, electrical AFM modes are an indispensable asset within the semiconductor and nanotechnology industries, enabling the characterization and manipulation of electrical properties at the nanoscale. However, electrical AFM measurements suffer from reproducibility issues caused, for example, by surface contaminations, Joule heating, and hard-to-minimize tip drift and tilt. Using as experimental system nanoscale Schottky diodes assembled on oxide-free silicon crystals of precisely defined surface chemistry, it is revealed that voltage-dependent adhesion forces lead to significant rotation of the AFM platinum tip. The electrostatics-driven tip rotation causes a strain gradient on the silicon surface, which induces a flexoelectric reverse bias term. This directional flexoelectric internal-bias term adds to the external (instrumental) bias, causing both an increased diode leakage as well as a shift of the diode knee voltage to larger forward biases. These findings will aid the design and characterization of silicon-based devices, especially those that are deliberately operated under large strain or shear, such as in emerging energy harvesting technologies including Schottky-based triboelectric nanogenerators (TENGs).

Molecular-level studies of extracellular matrix proteins conducted using atomic force microscopy.

Extracellular matrix (ECM) proteins provide anchorage and structural strength to cells and tissues in the body and, thus, are fundamental molecular components for processes of cell proliferation, growth, and function. Atomic force microscopy (AFM) has increasingly become a valuable approach for studying biological molecules such as ECM proteins at the level of individual molecules. Operational modes of AFM can be used to acquire the measurements of the physical, electronic, and mechanical properties of samples, as well as for viewing the intricate details of the surface chemistry of samples. Investigations of the morphology and properties of biomolecules at the nanoscale can be useful for understanding the interactions between ECM proteins and biological molecules such as cells, DNA, and other proteins. Methods for preparing protein samples for AFM studies require only basic steps, such as the immersion of a substrate in a dilute solution or protein, or the deposition of liquid droplets of protein suspensions on a flat, clean surface. Protocols of nanolithography have been used to define the arrangement of proteins for AFM studies. Using AFM, mechanical and force measurements with tips that are coated with ECM proteins can be captured in ambient or aqueous environments. In this review, representative examples of AFM studies are described for molecular-level investigations of the structure, surface assembly, protein-cell interactions, and mechanical properties of ECM proteins (collagen, elastin, fibronectin, and laminin). Methods used for sample preparation as well as characterization with modes of AFM will be discussed.

In situ spectroelectrochemical and nanomechanical studies in the atomic force microscopy mode of the oxidation—reduction processes of poly-N,N′-ethylenebis(3-methoxysalicylideneimine)

In situ spectroelectrochemical and nanomechanical studies in the atomic force microscopy mode of the oxidation—reduction processes of poly-N,N′-ethylenebis(3-methoxysalicylideneimine)

Characterization of composite materials with recycled wind turbine blade additives using atomic force microscopy

ABSTRACT The European Union’s efforts to increase the share of renewable energy translate into a growing number of wind farms. Post-operation wind turbines become increasing waste. Recycling wind turbine blades is a challenge due to the materials used (composites) and high costs. The article examines the influence of recyclate from wind turbine blades (derived from mechanical recycling) on the image of topography and Lateral Force Microscopy (LFM) in atomic force microscopy (AFM). Upon adding the recycled material, an increase in surface roughness is observed despite its prior polishing. The Young’s modulus determined from force spectroscopy (AFM mode) indicated a small difference in values between the matrix and reinforcement areas. This proves the significant influence of the primary and secondary interphase on the properties of secondary composites, which is an area for further research.

Probing Viscoelastic Properties and Interfaces in High-Density Polyethylene Vitrimers at the Nanoscale Using Dynamic Mode Atomic Force Microscopy.

Vitrimers are a new class of heterogeneous polymers that combine the best features of thermosets with those of thermoplastics. The introduction of cross-links strongly changes the viscoelastic behavior of vitrimer materials. However, the characterization and understanding of the nanostructures and interfaces in vitrimers resulting from dynamic cross-linking formation remain a major challenge. Here, using dynamic modes of atomic force microscopy (AFM), namely intermodulation AFM (ImAFM) and AFM-based dynamic mechanical analysis (AFM-nDMA), local viscoelastic properties and interfaces at the nanoscale length of high-density polyethylene (HDPE) vitrimer materials are reported. ImAFM imaging in combination with the k-means clustering algorithm clearly reveals two distinct phases in the vitrimer system with highly different viscoelastic properties. AFM-nDMA further provides quantitative nanoviscoelastic properties at the nanoscale to confirm that there is a cross-linking-rich aggregation area forming a nanosize network structure in the cross-linking-poor matrix phase. The cross-linking-rich region shows a similar elastic modulus but much higher adhesion force measured by AFM compared to the cross-linking-poor HDPE matrix. Furthermore, the frequency influence on the local viscoelastic properties of HDPE vitrimer at the nanoscale was initially screened. The observed HDPE vitrimer nanostructures and viscoelastic properties at the nanoscale also provide explanations on the observed bulk HDPE vitrimer crystallinity decrease and dimensional stability increase compared to HDPE. Therefore, probing the viscoelastic properties and interfaces of HDPE vitrimer provides important insights into understanding of the correlations between the vitrimer nanostructure and the bulk mechanical and rheological behaviors.

Thickness measurement of thin films using atomic force microscopy based scratching

Thin-film thickness measurements using atomic force microscopy (AFM) comprise two steps: 1. AFM scratching in order to produce an exposed film edge, and 2. subsequent AFM measurement of the corresponding step height across the exposed edge. Although the technique is known, many open questions have limited its wider applications. In order to clarify the open questions, here we first demonstrate how to determine the normal force applied during the scratching in contact mode needed to completely remove films from substrates. In order to determine film thickness from processed AFM images, we discuss two procedures based on the histogram method and polynomial step-function fitting. Mechanisms of the scratching process are elucidated by the analysis of lateral forces and their enhancement during the film peeling. Phase maps of scratched domains recorded in amplitude modulation AFM (tapping) mode display a clear contrast compared to pristine films. Therefore, we suggest their utilization as simple indicators of spatial domains with completely removed films. As an example, here the measurements were done on polymer films fabricated by layer-by-layer deposition of oppositely charged polyelectrolytes composed of poly(allylamine hydrochloride) and poly(sodium 4-styrenesulfonate), while the applicability of the presented method on other materials is discussed in detail.

Mixed-mode oscillations of an atomic force microscope in tapping mode.

In the phenomenon of mixed-mode oscillations, transitions between large-amplitude and small-amplitude oscillations may lead to anomalous jitter in the probe of a tapping mode atomic force microscope (TM-AFM) during the scanning process, thereby affecting the accuracy and clarity of the topographical images of the tested sample's surface. This work delves deeply into various mixed-mode oscillations and the corresponding formation mechanisms in TM-AFM under low-frequency resonant excitation. Through a detailed analysis of bifurcation sets of the fast subsystem, we found that the system's mixed-mode oscillations encompass the typical two coexisting branches and the novel three coexisting branches of equilibrium point attractors. In the stable case, a certain transition pattern in phase trajectory can be observed involving two jumps and four jumps, switching between quiescent and spiking states. In the bi-stable case, the trajectory undergoes distinct transitions decided by whether to pass through or crossover the middle branch of attractors when bifurcation occurs. By applying basin of attraction and fast-slow analysis methods, we unfold the dynamic mechanism of mixed-mode oscillations with distinct switching patterns. Our research contributes to a better understanding of complex oscillations of TM-AFM and provides valuable insights for improving image quality and measurement precision while mitigating detrimental oscillations.

Two operational modes of atomic force microscopy reveal similar mechanical properties for homologous regions of dystrophin and utrophin.

Duchenne muscular dystrophy (DMD) is a lethal muscle disease caused by the absence of the protein dystrophin. Dystrophin is hypothesized to work as a molecular shock absorber that limits myofiber membrane damage when undergoing reversible unfolding upon muscle stretching and contraction. Utrophin is a dystrophin homologue that is under investigation as a protein replacement therapy for DMD. However, it remains uncertain whether utrophin can mechanically substitute for dystrophin. Here, we compared the mechanical properties of homologous utrophin and dystrophin fragments encoding the N terminus through spectrin repeat 3 (UtrN-R3, DysN-R3) using two operational modes of atomic force microscopy (AFM), constant speed and constant force. Our comprehensive data, including the statistics of force magnitude at which the folded domains unfold in constant speed mode and the time of unfolding statistics in constant force mode, show consistent results. We recover parameters of the energy landscape of the domains and conducted Monte Carlo simulations which corroborate the conclusions drawn from experimental data. Our results confirm that UtrN-R3 expressed in bacteria exhibits significantly lower mechanical stiffness compared to insect UtrN-R3, while the mechanical stiffness of the homologous region of dystrophin (DysN-R3) is intermediate between bacterial and insect UtrN-R3, showing greater similarity to bacterial UtrN-R3.

Direct investigations of interactions between nucleolins and aptamers on pancreatic cancer and normal cells by atomic force microscopy

Nucleolin is overexpressed on the surface of pancreatic cancer cells and are regarded as the remarkable therapeutic target. Aptamers are capable of binding the external domain of nucleolin on the cell surface with high affinity and specificity. But nucleolin has not been localized on pancreatic cancer cells at very high spatial resolution, and the interactions between nucleolin and aptamers have not been investigated at very high force resolution level. In this work, nucleolin was localized on pancreatic cancer and normal cells by aptamers (9FU-AS1411-NH2, AS1411-NH2 and CRONH2) in Single Molecule Recognition Imaging mode of Atomic Force Microscopy. There are plenty of nucleolin on the surfaces of pancreatic cancer cells (area percentage about 5 %), while there are little nucleolin on the surfaces of normal cells. The interactions between three types of aptamers and nucleolins on the surfaces of pancreatic cancer cells were investigated by Single Molecule Force Spectroscopy. The unbinding forces of nucleolins-(9FU-AS1411-NH2) are larger than nucleolins-(AS1411-NH2). The dissociation activation energy on nucleolin-(9FU-AS1411-NH2) is higher than nucleolin-(AS1411-NH2), which indicates that the former complex is more stable and harder to dissociate than the later complex. There are no unbinding forces between nucleolin and CRONH2. All these demonstrate that nucleolin was localized on pancreatic cancer and normal cells at single molecule level quantitatively, and the interactions (unbinding forces and kinetics) between nucleolin and aptamers were studied at picoNewton level. The approaches and results of this work will pave new ways in the investigations of nucleolin and aptamers, and will also be useful in the studies on other proteins and their corresponding aptamers.

Balancing Ionic and Electronic Conduction at the LiFePO4 Cathode–Electrolyte Interface and Regulating Solid Electrolyte Interphase in Lithium‐Ion Batteries

AbstractRecently, in electric mobilities and stationary energy storage device applications, the development of long‐lasting, low‐cost, and high‐safety lithium‐ion batteries (LIBs) is widely studied. LiFePO4 (LFP) is a core cathode material for LIBs owing to its cost‐effectiveness and high safety. However, it exhibits low electronic conductivity and sluggish Li+ diffusion, hindering the application of LFP cathodes in high‐power battery industries. Herein, a triazole‐motivated electrolyte additive, 1‐(trimethylsilyl)−1H‐benzotriazole (TMSBTA) is presented, for mitigating iron dissolution via HF scavenging, reinforcing the robustness of the solid electrolyte interphase and constructing a cathode–electrolyte interface (CEI) to balance the ion and electron conduction of the CEI on the LFP cathode. Scanning probe microscopy performed in the conductive atomic force microscopy mode indicates that the electronically conductive CEI created by the oxidative decomposition of TMSBTA enables rapid and homogeneous lithiation and delithiation during cycling without morphological changes in the LFP particles. This study elucidates the design principles of the CEI on the LFP cathode and is expected to guide integrated electrolyte additive engineering for LFP‐containing LIBs.

A scanning probe microscope compatible with quantum sensing at ambient conditions.

We designed and built up a new type of ambient scanning probe microscope (SPM), which is fully compatible with state-of-the-art quantum sensing technology based on the nitrogen-vacancy (NV) centers in diamond. We chose a qPlus-type tuning fork (Q up to ∼4400) as the current/force sensor of SPM for its high stiffness and stability under various environments, which yields atomic resolution under scanning tunneling microscopy mode and 1.2-nm resolution under atomic force microscopy mode. The tip of SPM can be used to directly image the topography of nanoscale targets on diamond surfaces for quantum sensing and to manipulate the electrostatic environment of NV centers to enhance their sensitivity up to a single proton spin. In addition, we also demonstrated scanning magnetometry and electrometry with a spatial resolution of ∼20nm. Our new system not only paves the way for integrating atomic/molecular-scale color-center qubits onto SPM tips to produce quantum tips but also provides the possibility of fabricating color-center qubits with nanoscale or atomic precision.

Multiparametric AFM insights into electron transport mechanisms in biomemristors

Biomemristors have attracted significant attention due to their applications in biodegradable and flexible electronic devices, and their prospective functions in information storage, neural synapses, and neuromorphic computation. Hence, understanding biomaterials' resistive switching (RS) mechanism is essential to design novel biomemristors with enhanced performance. In the last decade, various atomic force microscopy (AFM) modes, such as Kelvin probe force microscopy (KPFM) and conductive atomic force microscopy (cAFM), in situ/operando visualize the electron transport behaviors within biomemristors at the nanoscale. This review provides a comprehensive discussion of multiparametric AFM techniques to characterize biomemristors and inspire new ideas in developing next-generation consumer electronics. We also summarize the progress of revealing the internal mechanism of biomemristors with functional AFM to visualize and understand the switching behavior. Finally, the opportunities and challenges of further utilizing multiparametric AFM to explore the electron transport mechanisms in biomemristors are presented.

Direct investigations of the effects of nicardipine on calcium channels of astrocytes by Atomic Force Microscopy

Calcium channel blockers (CCB) of astrocytes can blockade the calcium ions entry through the voltage gated calcium channels (VGCC), and is widely used in the diseases related with VGCC of astrocytes. But many aspects of the interaction mechanisms between the CCB and VGCC of astrocytes still remain unclear due to the limited resolution of the approaches. Herein the effects of the nicardipine (a type of CCB) on VGCC of astrocytes were investigated at very high spatial, force and electrical resolution by multiple modes of Atomic Force Microscopy (AFM) directly. The results reveal that after the addition of nicardipine, the recognition signals of VGCC disappeared; the specific unbinding forces vanished; the conductivity of the astrocytes decreased (the current decreased about 2.9 pA and the capacitance was doubled); the surface potential of the astrocytes reduced about 14.2 mV. The results of electrical properties investigations are consistent with the simulation experiments. The relations between these biophysical and biochemical properties of VGCC have been discussed. All these demonstrate that the interactions between nicardipine and VGCC have been studied at nanometer spatial resolution, at picoNewton force resolution and very high electrical signal resolution (pA in current, pF in capacitance and 0.1 mV in surface potential) level. The approaches are considered to be high resolution and high sensitivity, and will be helpful and useful in the further investigations of the effects of other types of CCB on ion channels, and will also be helpful in the investigations of mechanisms and therapy of ion channelopathies.

Atomic Force Microscopy (AFM) Tip based Nanoelectrode with Hydrogel Electrolyte and Application to Single-Nanoparticle Electrochemistry

<p>An unconventional fabrication technique of nanoelectrode was developed using atomic force microscopy (AFM) and hydrogel. Until now, the precise control of electroactive area down to a few nm<sup>2</sup> has always been an obstacle, which limits the wide application of nanoelectrodes. Here, the nanometer-sized contact between the boron-doped diamond (BDD) as conductive AFM tip and the agarose hydrogel as solid electrolyte was well governed by the feedback amplitude of oscillation in the non-contact mode of AFM. Consequently, this low-cost and feasible approach gives rise to new possibilities for the fabrication of nanoelectrodes. The electroactive area controlled by the set point of AFM was investigated by cyclic voltammetry (CV) of the ferrocenmethanol (FcMeOH) combined with quasi-solid agarose hydrogel as an electrolyte. Single copper (Cu) nanoparticle was deposited at the apex of the AFM tip using this platform whose electrocatalytic activity for nitrate reduction was then investigated by CV and Field Emission-Scanning Electron Microscopy (FE-SEM), respectively.</p>

Special contribution of atomic force microscopy in cell death research

Abstract Cell death is an important life activity in individual development. Changes in morphological and mechanical properties during cell death are crucial to identify the modes of cell death. However, due to technical limitations, little is known about these characteristics. The emergence of atomic force microscopy (AFM), a nanoscale research tool that integrates imaging and mechanical measurement functions, provides new insights into our understanding of cell death. Based on a brief introduction to the structure, principle, and working modes of AFM, this article elaborates on the contribution of AFM in cell death to detect morphological and mechanical properties, especially in apoptotic cells. Meanwhile, the potential of AFM in distinguishing different cell death modes and visualizing membrane pores (medicated by apoptosis and pyroptosis) is illustrated. In addition, this article states that using single-molecule force spectroscopy by AFM to study the mechanical and adhesive properties of cell death-related molecules. Finally, we discuss the challenges facing and further perspective of AFM.

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.

Dual Friction Force/Fluorescence Microscopy.

Friction force microscopy (FFM) is a mode of atomic force microscopy (AFM) that quantifies both normal and horizontal forces against substrates. Recent improvement in its accuracy at nanonewton ranges and the possibility of combining AFM with fluorescence microscopy enabled the simultaneous characterization by FFM and fluorescence microscopy. This Tutorial describes the operation principle of the dual friction force/fluorescence microscopy setup and highlights its emerging applications in mechanochromic materials.

Energy dissipation of a contact line moving on a nanotopographical defect.

Understanding the origin of the dissipative mechanisms that control the dynamics of a contact line is a real challenge. In order to study the energy dissipation at the contact line when a moving meniscus encounters topographical defects, we developed atomic force microscopy (AFM) experiments using nanofibers with nanometer scale defects. These experiments realized with three liquids are performed in two AFM modes: the contact mode (C-AFM) is used to measure the energy associated with the contact angle hysteresis in the limit of a static situation, deduced from advancing and receding dipping experiments on an isolated defect; the frequency-modulation mode (FM-AFM) is performed at different amplitudes and then velocities to measure the energy dissipated as the contact line moves over the same defect. Strong dissipation peaks appear above a threshold amplitude characteristic of the liquid and the defect, which is determined by the width of the hysteresis measured in statics. Furthermore, the dissipation energy of the moving contact line measured in dynamics is equal to the hysteresis capillary energy whatever the amplitude and is therefore independent of the contact line velocity. These results point out that the defect contribution to dissipation energy of a moving contact line on real surfaces is only governed by the pinning-depinning energy with no contribution of viscous effects.

Enhancing nanoscale viscoelasticity characterization in bimodal atomic force microscopy.

Polymeric, soft, and biological materials exhibit viscoelasticity, which is a time dependent mechanical response to deformation. Material viscoelasticity emerges from the movement of a material's constituent molecules at the nano- and microscale in response to applied deformation. Therefore, viscoelastic properties depend on the speed at which a material is deformed. Recent technological advances, especially in atomic force microscopy (AFM), have provided tools to measure and map material viscoelasticity with nanoscale resolution. However, to obtain additional information about the viscoelastic behavior of a material from such measurements, theoretical grounding during data analysis is required. For example, commercially available bimodal AFM imaging maps two different viscoelastic properties of a sample, the storage modulus, E', and loss tangent, tan δ, with each property being measured by a different resonance frequency of the AFM cantilever. While such techniques provide high resolution maps of E' and tan δ, the different measurement frequencies make it difficult to calculate key viscoelastic properties of the sample such as: the model of viscoelasticity that describes the sample, the loss modulus, E'', at either frequency, elasticity E, viscosity η, and characteristic response times τ. To overcome this difficulty, we present a new data analysis procedure derived from linear viscoelasticity theory. This procedure is applied and validated by performing amplitude modulation-frequency modulation (AM-FM) AFM, a commercially available bimodal imaging technique, on a styrene-butadiene rubber (SBR) with known mechanical behavior. The new analysis procedure correctly identified the type of viscoelasticity exhibited by the SBR and accurately calculated SBR E, η, and τ, providing a useful means of enhancing the amount of information gained about a sample's nanoscale viscoelastic properties from bimodal AFM measurements. Additionally, being derived from fundamental models of linear viscoelasticity, the procedure can be employed for any technique where different viscoelastic properties are measured at different and discrete frequencies with applied deformations in the linear viscoelastic regime of a sample.