Tapping Mode Atomic Force Microscopy Research Articles

Enhancing multiple harmonics in tapping mode atomic force microscopy by added mass with finite size

A method to enhance the harmonics of tapping mode atomic force microscopy is proposed in this study through an attached mass with finite size. It is demonstrated that ratios between higher-order natural frequencies and the fundamental one can be tuned to be specified integers with this method. The first three eigenmodes could be excited simultaneously, defining a highly-sensitive multi-harmonic cantilever, which can be utilized to resolve the sample properties effectively. The established theoretical model is validated by finite element analysis. This method can also be developed for the determination of mass, position and geometry of micro-particle in mass sensing application.

Imaging the Substructures of Individual IgE Antibodies with Atomic Force Microscopy.

The interactions between antibodies and substrates directly affect their conformations and thus their immune functions. Therefore, it is desirable to study the structures of antibodies at the single molecule level. Herein, the substructures of Immunoglobulin E (IgE) on solid surfaces were investigated. For this purpose, tapping-mode atomic force microscopy (AFM) was applied to observe individual IgE substructures adsorbed onto Mg2+ and Na+ modified mica substrates in air. As expected, the AFM images revealed that the IgE antibodies exhibited different conformations on the surface of mica substrate consisting of the four basic orientations: three domain, two equivalent domain, two unequal domain, and single domain morphologies. Moreover, the differences in the different orientations in single IgE antibodies were also identified clearly.

Scan Rate Adaptation for AFM Imaging Based on Performance Metric Optimization

Constant-force contact-mode atomic force microscopy (AFM) relies on a feedback control system to regulate the tip-sample interaction during imaging. Due to limitations in actuators and control, the bandwidth of the regulation system is typically small. Therefore, the scan rate is usually limited in order to guarantee a desirable image quality for a constant-rate scan. By adapting the scan rate online, further performance improvement is possible, and the conditions to this improvement have been explored qualitatively in a previous study for a wide class of possible scan patterns. In this article, a quantitative assessment of the previously proposed adaptive scan scheme is investigated through experiments that explore the impact of various degrees of freedom in the algorithm. Further modifications to the existing scheme are proposed and shown to improve the closed-loop performance. The flexibility of the proposed approach is further demonstrated by applying the algorithm to tapping-mode AFM.

Humidity-Dependent Surface Structure and Hydroxide Conductance of a Model Quaternary Ammonium Anion Exchange Membrane

Anion exchange membrane (AEM) fuel cells (AEMFCs) are a promising cost-effective alternative energy conversion technology because of the potential implementation of earth-abundant catalysts, obviating the need for precious metals. AEMs, however, have low conductivity and suffer from poor stability. The conductivity of the AEM is inherently tied to the complex phase-separated morphology, as its dependence on the hydration level is not well understood. In this report, we employ phase-contrast tapping mode and conductive-probe atomic force microscopy (cp-AFM) to study the nanoscale surface morphology and hydroxide conductance of a commercially available quaternary ammonium (QA) AEM by FuMA-Tech GmbH (Fumapem FAA-3). The chemical structure of FAA-3 consists of a poly(phenylene oxide) backbone with QA functionality. The morphology of FAA-3 was observed in the bromide (FAA-3-Br-) and hydroxide form (FAA-3-OH-) in dehydrated and hydrated conditions. Under dehydrated conditions, both membranes showed no phase contrast, indicating the absence of phase-separated hydrophilic domains at the surface. At hydrated conditions, FAA-3-Br- shows randomly dispersed isolated clusters, while FAA-3-OH- shows elongated fibrillar structures extending microns in length. cp-AFM of hydrated FAA-3-OH- showed that these elongated regions were insulating. These results provide morphological evidence for the conduction of hydroxide at the surface and its dependence on the hydration level.

Effect of Wetting and Dewetting Dynamics on Atomic Force Microscopy Measurements.

Water bridge dynamics between an atomic force microscopy (AFM) tip and a flat substrate is studied by using a multibody dissipative particle dynamics (MDPD) model. First, the numerical model is validated by comparing the present results of droplet contact angles and liquid bridges with those reported in the literature. Then, the ability of MDPD to capture the meniscus shape and behavior for different operating conditions and geometric parameters is examined for both static and dynamic cases. Hence, several parametric studies and analyses of the AFM tip configuration and its operating conditions are reported. It is found that a critical capillary number of about 0.001 is calculated based on 5% change on the force measurements between the static and dynamic results. It is also demonstrated that the hysteresis behavior in the capillary force exerted on the AFM tip can be successfully predicted by using the MDPD model when the tip approaches or retracts from the substrate. Moreover, there is an excellent agreement in the results of breakup distance for different water bridge volumes between the predictions of the MDPD model and the theory. Also, the hysteresis of capillary force exerted on an AFM tip composed of multibody design is studied. The prediction on the transition of the capillary force vs distance between the AFM tip and the substrate is in good agreement with the experimental results. Therefore, we demonstrate a validated MDPD model which can successfully capture liquid bridge dynamics. This model can be used as a powerful design tool for meniscus manipulation technology, such as dip-pen nanolithography, as well as for studying dynamic, e.g., tapping mode AFM tip, interactions with a liquid bridge.

Understanding of Molecular Contribution of Quinhydrone/Methanol Organic Passivation for Improved Minority Carrier Lifetime on Nanostructured Silicon Surface

In this report, we present a study of the quinhydrone/methanol (QHY/MeOH) organic passivation technique for a silicon (Si) surface. The roles of p-benzoquinone (BQ) and hydroquinone (HQ), which make up QHY, in controlling the uniformity and coverage of the passivation layer as well as the minority carrier lifetime (τeff) of Si were investigated. The uniformity and coverage of the passivation layer after treatment with diverse mixture ratios of BQ and HQ in MeOH were studied with two different atomic force microscope (AFM) techniques, namely tunneling mode (TUNA) and high-resolution tapping mode AFM (HR-AFM). In addition, the τeff and surface potential voltages (SPV) of passivated surfaces were measured to clarify the relationship between the morphologies of the passivation layers and degrees of surface band bending. The molecular interactions between BQ and HQ in MeOH were also analyzed using Fourier-transform infrared spectroscopy (FT-IR). In our study, we successfully demonstrated the role of each molecule for effective Si surface passivation with BQ working as a passivation agent and HQ contributing as a proton (H+) donator to BQ for accelerating the passivation rate. However, our study also clearly revealed that HQ could also hinder the formation of a conformal passivation layer, which raises an issue for passivation over complex surface geometry, especially a nanostructured surface.

Effects of Elastic Restraints on the Fundamental Frequency of Nonlocal Nanobeams with Tip Mass

The fundamental frequencies of an elastically restrained nanobeam with a tip mass are studied based on the nonlocal Euler-Bernoulli beam theory. The nanobeam has a torsional spring at one end and a translational spring at the other end where a tip mass is attached. The aim is to model a tapping mode atomic force microscope (TM-AFM), which can be utilized in imaging and the manufacture of Nano-scale structures. A TM-AFM uses high frequency oscillations to remove material, shape structures or scan the topology of a Nano-scale structure. The nonlocal theory is effective at modelling Nano-scale structures, as it takes small scale effects into account. Torsional elastic restraints can model clamped and pinned boundary conditions, as their stiffness values change between zero and infinity. The effects of the stiffness of the elastic restraints, tip mass and the small-scale parameter on the fundamental frequency are investigated numerically.

The Effect of Water Concentration in Carbonate-Based Electrolytes on the Si Anode/Electrolyte Interface

Lithium-ion batteries (LiBs) have been successfully utilized as power sources in various applications ubiquitous in our daily lives, ranging from portable electronic devices to electric vehicles. To meet the increasing energy demand, however, development of LiBs with a higher energy density is inevitable. Using silicon (Si) as an anode is promising due to its high theoretical capacity (approximately 4200 mAhg-1), appropriate operating voltage (~0.4 V vs. Li/Li+), abundance, and environmentally benign nature.1 Despite the aforementioned advantages, several challenges remain before the commercial utilization of Si anodes, namely the low conductivity of its readily-formed surface oxide (SiO2), a large volume change (up to 400 %) during lithiation/delithiation, and the instability of Si/electrolyte interface (SiEI).2-3 As the large volume change leads to fracture and continuous evolution of SiEI, achieving a stable SiEI is a key to developing successful LiBs with Si anodes. Water, which is known to react with LiPF6 salt in carbonate-based electrolytes to generate corrosive hydrofluoric acid (HF),4 is a source for the electrode/electrolyte interface destabilization. Thus, it is essential to understand how the presence of even trace amounts of water in the system affects the interfacial chemistry of the LiB electrodes. While the performance of LiBs with graphite or lithium titanate negative electrodes have been previously studied with excess water in the electrolyte,5-6 information on the effect of water concentration in the electrolyte on Si anodes, and the SiEI in particular, is limited. In this work, we evaluated the electrochemical performance of Si anodes in a standard electrolyte (1.2 M LiPF6 in EC:EMC (3:7 wt%)) with varying concentration of water (10 - 1,000 ppm). Subsequent analyses on the cycled Si anodes were performed utilizing a variety of surface and bulk characterization techniques. The surface chemistry (e.g., composition and evolution) of SiEI was analyzed using Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, time-of-flight secondary ion mass spectrometry (TOF-SIMS), and X-ray photoelectron spectroscopy (XPS). Surface morphologies of cycled Si anodes were measured with tapping-mode atomic force microscopy (AFM), and the surface resistivities were mapped in contact-mode with scanning spreading resistance microscopy (SSRM). The information obtained is utilized to understand water concentration effects on the properties, reactivity, and evolution of the SiEI and the electrochemical cell performance. References Feng, K.; Li, M.; Liu, W.; Kashkooli, A. G.; Xiao, X.; Cai, M.; Chen, Z., Silicon-Based Anodes for Lithium-Ion Batteries: From Fundamentals to Practical Applications. Small 2018, 14 (8), 1702737.Chae, S.; Ko, M.; Kim, K.; Ahn, K.; Cho, J., Confronting Issues of the Practical Implementation of Si Anode in High-Energy Lithium-Ion Batteries. Joule 2017, 1 (1), 47-60.Philippe, B.; Dedryvere, R.; Allouche, J.; Lindgren, F.; Gorgoi, M.; Rensmo, H.; Gonbeau, D.; Edstrom, K., Nanosilicon Electrodes for Lithium-Ion Batteries: Interfacial Mechanisms Studied by Hard and Soft X-ray Photoelectron Spectroscopy. Chem. Mater. 2012, 24 (6), 1107-1115.Xu, K., Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries. Chem. Rev. 2004, 104 (10), 4303-4417.Burns, J. C.; Sinha, N. N.; Jain, G.; Ye, H.; VanElzen, C. M.; Scott, E.; Xiao, A.; Lamanna, W. M.; Dahn, J. R., The impact of intentionally added water to the electrolyte of Li-ion cells. I. Cells with graphite negative electrodes. J. Electrochem. Soc. 2013, 160 (11), A2281-A2287.Burns, J. C.; Sinha, N. N.; Jain, G.; Ye, H.; Van Elzen, C. M.; Scott, E.; Xiao, A.; Lamanna, W. M.; Dahn, J. R., The impact of intentionally added water to the electrolyte of Li-ion cells: II. Cells with lithium titanate negative electrodes. J. Electrochem. Soc. 2014, 161 (3), A247-A255.

$Q$ Control of an Active AFM Cantilever With Differential Sensing Configuration

Microcantilevers featuring separate built-in actuation and displacement sensing capabilities allow effective and simple implementation of control methods, opening a pathway to achieving higher scan speeds in tapping-mode atomic force microscopy. Such active cantilevers are a significant milestone to eventually obtain video-rate on-chip atomic force microscopes (AFMs) that can even surpass the functionality and imaging speed of their macroscale counterparts at a significantly lower cost. In this brief, we present an active AFM cantilever with an on-chip actuator and two built-in displacement sensors, designed to be integrated into on-chip AFMs. The common feedthrough problem present in this type of architecture is addressed by a differential sensing configuration, and the revealed dynamics are used for the system identification. A positive position feedback controller is designed to actively tailor the $Q$ factor of the cantilever. The imaging performance of the microcantilever with and without $Q$ control is compared by attenuating the cantilever’s $Q$ factor from 177 to 15 using the feedback loop. A common artifact in high-speed scans, the parachuting effect, is mitigated, rendering higher imaging speeds achievable.

Nanofluidic chromatography using a vibrating atomic force microscope tip.

The separation of liquid mixtures is demonstrated using the vibrating tip of an Atomic Force Microscope (AFM). Fluid is collected onto the tip from a liquid surface while under tapping mode operation. This suppresses bulk capillary flow and enhances partitioning based on molecular affinity to the tip. AFM tapping mode separation was tested on liquid films consisting of binary and complex mixtures. The separated components were analyzed using tip enhanced infrared spectroscopy and direct analysis in real time mass spectrometry. The results demonstrate nanometer scale chemical separation for ultratrace analysis and nanofluidic applications.

High Temperature Polymer Electrolyte Membrane Achieved By Grafting Poly(1-vinylimidazole) on Polysulfone for Fuel Cell Applications

High temperature polymer electrolyte membranes with phosphoric acid doping are crucial materials of high temperature fuel cells. However, the evolution of the type membrane is suffering from the trade-off between proton conductivity and mechanical strength, because high proton conductivity requires high phosphoric acid doping level, which will reduce the mechanical properties due to the plasticization of phosphoric acid on polymer backbone. Here, a new strategy is employed to respond to the unresolved challenges by grafting poly(1-vinylimidazole) as phosphoric acid doping sites on polysulfone backbone via atom transfer radical polymerization. Then poly(1-vinylimidazole) grafted polysulfone membrane with different length of side chains is obtained and soaked in phosphoric acid to work as high temperature polymer electrolyte membrane. The tapping-mode AFM images and 1-D SAXS result of PA doped membrane suggest the formation of micro-phase separated structures, and the ionomer peaks shift from 1.34 nm-1 to 1.19 nm-1 with increasing the length of side chain, corresponding to d-spacing of 4.67 nm and 5.28 nm, respectively. Therefore, the prepared phosphoric acid doped membranes possess excellent proton conductivity of 127 mS cm-1 under 160 °C due to the structure, while mechanical properties are retained due to the reduction of plasticizing effect caused by the separation of phosphoric acid adsorption sites and polymer backbone, presenting an outstanding tensile strength of 7.94 MPa. Meanwhile, the impressive fuel cell performance with the membranes is gained, reaching a maximum peak power density of 559 mW cm-2 under 160 oC. More importantly, the work provides a new sight to solve the trade-off between proton conductivity and mechanical strength for phosphoric acid doped high temperature polymer electrolyte membranes. Figure 1

Thin‐film nanostructure and polymer architecture in semicrystalline syndiotactic poly(p‐methylstyrene)–(cis‐1,4‐polybutadiene) multiblock copolymers

AbstractThe thin‐film morphology of stereoregular syndiotactic poly(p‐methylstyrene)–(cis‐1,4‐polybutadiene) (sP(pMS–B)) multiblock copolymers has been investigated using tapping mode atomic force microscopy with variation of the polymer composition and monomer block lengths. The morphology of the thin films ranges from isolated circular domains of sP(pMS) embedded into a matrix of polybutadiene (PB) to isolated domains of PB embedded into a matrix of sP(pMS), passing through bicontinuous (jagged) lamellae when the pMS concentration is in the range 20–67 mol%. Multiple folding of the polymer segments, i.e. where reciprocal inclusions of polymer segments to each other phase are able to generate greater domain, has been postulated and validated by considerations on the polymer architecture and the thermal and crystalline behaviour. © 2019 Society of Chemical Industry

A comprehensive model for transient behavior of tapping mode atomic force microscope

Many investigations have focused on steady-state nonlinear dynamics of cantilevers in tapping mode atomic force microscopy (TM-AFM). However, a transient dynamic model—which is essential for a model-based control design—is still missing. In this paper, we derive a mathematical model which covers both the transient and steady-state behavior. The steady-state response of the proposed model has been validated with existing theories. Its transient response, however, which is not covered with existing theories, has been successfully verified with experiments. Besides enabling model-based control design for TM-AFM, this model can explain the high-end aspects of AFM such as speed limitation, image quality, and eventual chaotic behavior.

Robustness of attractors in tapping mode atomic force microscopy

In this work, we perform a comprehensive analysis of the robustness of attractors in tapping mode atomic force microscopy. The numerical model is based on cantilever dynamics driven in the Lennard–Jones potential. Pseudo-arc-length continuation and basins of attraction are utilized to obtain the frequency response and dynamical integrity of the attractors. The global bifurcation and response scenario maps for the system are developed by incorporating several local bifurcation loci in the excitation parameter space. Moreover, the map delineates various escape thresholds for different attractors present in the system. Our work unveils the properties of the cantilever oscillation in proximity to the sample surface, which is governed by the so-called in-contact attractor. The robustness of this attractor against operating parameters is quantified by means of integrity profiles. Our work provides a unique view into global dynamics in tapping mode atomic force microscopy and helps establishing an extended topological view of the system.

MoS2 Field-Effect Transistor-Amyloid-β1-42 Hybrid Device for Signal Amplified Detection of MMP-9.

The detection of circulating protein (CP) is very important for the diagnosis and therapeutics of cancer. Conventional techniques based on a specific antibody-antigen interaction are still lacking because of a shortage of cost effectiveness, complicated sandwich structure and tagging process, and inconsistent detection of CP due to the inherent instability of antibodies. Herein, we demonstrate a hybrid device consisting of two-dimensional (2D) nanoscale molybdenum disulfide (MoS2) field-effect transistor (FET) with an amyloid-β1-42 (Aβ1-42) functionalized surface, which amplifies electric signals of the FET in order to detect matrix metalloproteinase-9 (MMP-9), which is a certain type of CP that degrades Aβ1-42. With the hybrid device, we detected the concentrations of MMP-9 in the range from 1 pM to 10 nM. Moreover, using tapping-mode atomic force microscopy and Kelvin probe force microscopy, we verified that the signal amplification corresponding to the MMP-9 concentrations was caused by the reduced length and the decreased surface potential of degraded Aβ1-42 due to MMP-9. The hybrid device studied in this paper can be very useful for monitoring MMP-9 activity, as well as serving as a sensing platform for the electrical signal amplification of 2D MoS2 FET-biosensors.

Low-Temperature Deposition of Inorganic–Organic HfO2–PMMA Hybrid Gate Dielectric Layers for High-Mobility ZnO Thin-Film Transistors

Low-temperature solution-processed inorganic–organic hybrid gate dielectrics are considered as emerging candidates for future low-cost flexible electronic devices, which are alternatives to high-temperature inorganic-based gate dielectric materials. In the present work, we developed a novel inorganic–organic HfO2–PMMA hybrid dielectric material by an efficient eco-friendly sol–gel method, deposited by spin-coating technique and converted into dielectric thin films at a very low thermal annealing temperature of 185 °C. The HfO2–PMMA hybrid thin-film formation was systematically investigated by FTIR and XPS techniques. Subsequently, a very low surface roughness of 0.8 nm and high uniformity of hybrid thin films were observed by tapping-mode AFM. Also, the thin films showed a hydrophilic nature with a high surface energy of 59.9 mJ/m2 as observed by the contact angle technique. The insulating properties of this hybrid film, studied by C–V and I–V measurements, showed very low leakage current density under 1 ...

Measurement of Radial Elasticity and Original Height of DNA Duplex Using Tapping-Mode Atomic Force Microscopy.

Atomic force microscopy (AFM) can characterize nanomaterial elasticity. However, some one-dimensional nanomaterials, such as DNA, are too small to locate with an AFM tip because of thermal drift and the nonlinearity of piezoelectric actuators. In this study, we propose a novel approach to address the shortcomings of AFM and obtain the radial Young’s modulus of a DNA duplex. The elastic properties are evaluated by combining physical calculations and measured experimental results. The initial elasticity of the DNA is first assumed; based on tapping-mode scanning images and tip–sample interaction force simulations, the calculated elastic modulus is extracted. By minimizing the error between the assumed and experimental values, the extracted elasticity is assigned as the actual modulus for the material. Furthermore, tapping-mode image scanning avoids the necessity of locating the probe exactly on the target sample. In addition to elasticity measurements, the deformation caused by the tapping force from the AFM tip is compensated and the original height of the DNA is calculated. The results show that the radial compressive Young’s modulus of DNA is 125–150 MPa under a tapping force of 0.5–1.3 nN; its original height is 1.9 nm. This approach can be applied to the measurement of other nanomaterials.

Effect of furnace annealing on the ferroelectricity of Hf0.5 Zr0.5O2 thin films

The effect of furnace annealing on the ferroelectricity and crystal phase of Hf0.5ZrO2 (HZO) ultrathin films is studied as a function of film thickness. HZO films are deposited using atomic layer deposition (ALD) in a Ge-HZO-TiN stack with Pt as the top contact electrode. Furnace annealing is carried out after crystallizing the films with rapid thermal annealing in the presence of a TiN capping electrode. While furnace annealing did not have much impact on the 108 ALD cycles (~11 nm) film, it enhanced the ferroelectricity of the 44 ALD cycles film (~4.5 nm). Positive-up-negative-down tests provide evidence of ferroelectricity in the 40 ALD cycles (~4 nm) furnace annealed film after cycling the film at higher fields. Grazing incidence X-ray diffraction shows that the non-centrosymmetric orthorhombic phase responsible for ferroelectricity increased after furnace annealing in thinner films, but little change occurred in the 108 ALD cycles film that was rich in orthorhombic phase prior to furnace annealing. An analysis of the HZO films with a tapping mode atomic force microscope shows grain growth in the 44, and 40 ALD cycles films after furnace annealing.

Synthesis of a Rod-rod Diblock Copolymer, Poly(3-hexylthiophene)-block-poly(furfuryl isocyanate), through the Anionic Polymerization with an Oxyanionic Macroinitiator

A rod-rod diblock copolymer (diBCP), poly(3-hexylthiophene)-block-poly(furfuryl isocyanate) (P3HT-b-PFIC), was synthesized through the anionic polymerization with an oxyanionic macroinitiator of P3HT. The properties of the diBCP (molecular weight, dispersity, composition, thermal stability, UV-visible absorption, and thin film morphology) were determined by various analytical methods. P3HT-b-PFIC was blended with C60 in a toluene solution to prepare a thin film of binary electron donor/acceptor system. Such blending enabled partial conjugation of the two components by the Diels-Alder reaction between furan and C60 at 60 °C for 3 h; the mixture was then spin-cast as a thin film, and annealed at 250 °C for 24 h. Tapping-mode atomic force microscopy (AFM) revealed that P3HT and C60 domains had nanoscale interfaces without a large phase segregation. This result indicated that the microphase separation of C60-functionalized P3HT-b-PFIC preserved even at high temperature provided free C60 molecules with channels to diffuse on the sides of P3HT domain, thus preventing the macroscopic crystallization of free C60 through the interfacial stabilization.

Nickel Nanofilms Electrolessly Deposited on Organosilane Nanorings and Characterized by Contact Mode AFM Combined with Magnetic Sample Modulation

Surface structures of magnetic nanorings were made using electroless deposition of Ni onto patterned templates of an amine-functionalized organosilane. Samples were prepared by chemical approaches based on colloidal lithography employing a surface mask of size-sorted, monodisperse silica spheres. Surface changes were evaluated after key points of the reactions using imaging modes of atomic force microscopy (AFM). Nanopatterns of 3-aminopropyltriethoxysilane (APTES) were prepared on Si(111) by applying a heated vapor to a surface mask of silica spheres. After rinsing, the particle mask was removed to reveal ring-shaped nanopatterns presenting amine groups at the interface. Organosilane nanopatterns were then immersed in a solution of Pd catalyst followed by treatment in a Ni plating bath. Changes in surface morphology after each reaction step were characterized ex situ using tapping-mode AFM to follow the time course of nanofabrication. Images of the Ni nanorings acquired with AFM were compared with SEM micrographs to further elucidate the morphology of the metal coatings. The magnetic character of the nanostructures was investigated with magnetic sample modulation (MSM-AFM), which is a hybrid of contact mode AFM combined with magnetic actuation of samples. Surface maps of the vibration of diamagnetic Pd and magnetic Ni nanorings were obtained with MSM-AFM, providing insight on processes of electroless plating. Fine details of the surface corrugation and grain structure of the Ni coated areas of the sample detected with SEM were sensitively resolved with MSM-AFM that were not apparent in AFM topography frames. Chemistry-based steps with electroless deposition (ELD) of metal and colloidal lithography provide a practical route for reproducible nanofabrication of highly regular geometries with high-throughput.