Multimodal Atomic Force Microscopy Research Articles

Nondestructive Nano-Imaging and Nano-Spectroscopy of Buried Battery Interfaces: Advancing in Situ and Operando Infrared Characterization Schemes for Basic Energy Storage Science

A critical component to the advancement and realization of beyond Li-ion electrical energy storage technologies is the careful study and characterization of the electrochemically active interfaces that govern the function and performance of such devices. Ideally, characterization of interfaces, and the interphases that grow therein, would be done in an inherently non-destructive way, while within its undisturbed native environment, and with nanoscale resolution over microscale areas (to resolve the kinds, and distribution, of the interphase building blocks). The practical realization of this, though, is extremely challenging because these interfaces and interphases are buried, highly reactive, nano-thin, and structurally and chemically heterogenous.In this talk, we’ll discuss a brief history of an emerging and evolving infrared near-field methodology aimed at overcoming as many of these challenges as possible, to study electrochemical energy storage materials and interfaces in their native environment, non-destructively, and with nanoscale resolution. This is accomplished by employing a combination of precisely engineered and electrochemically controlled graphene/electrolyte interfaces, and diffraction-limit-breaking near-field optical probes capable of chemical imaging and vibrational spectroscopy at the nanoscale. We will present works published on graphene/liquid-electrolyte interfaces,1 and anode-free-based Li/polymer-electrolyte interfaces.2 We will show that in the former case, operando potential step voltammetry + nano-FTIR is capable of sensing concentration changes in the electric double layer.1 Furthermore, in the latter case, where we will spend most our time, in situ multimodal nano-FTIR, ATR-FTIR, infrared nano-imaging, and atomic force microscopy reveal nanoscale structural and chemical heterogeneities intrinsic to the solid polymer electrolyte initiate a cascade of additional interfacial nanoscale heterogeneities during Li plating and stripping, including Li-ion conductivity, electrolyte decomposition, and interphase formation.2 1.) Y.-H. Lu,* J.M. Larson,* A. Baskin, X. Zhao, P. Ashby, D. Prendergast, H. Bechtel, R. Kostecki, and M. Salmeron, Nano Lett 19, 5388-5393 (2019). 2.) X. He*, J. M. Larson*, H. A. Bechtel, and R. Kostecki, Nat Commun, 13, 1398 (2022).(*: Denotes Equal Contribution) Figure 1

Characterization of quantum dot-like emitters in programmable arrays of nanowrinkles of 1L-WSe2

When combined with nanostructured substrates, two-dimensional semiconductors can be engineered with strain to tailor light–matter interactions on the nanoscale. Recently, room-temperature nanoscale exciton localization with controllable wrinkling in 1L-WSe2 was achieved using arrays of gold nanocones. Here, the characterization of quantum dot-like states and single-photon emitters in the 1L-WSe2/nanocone system is reported. The nanocones induce a wide range of strains, and as a result, a diverse ensemble of narrowband, potential single-photon emitters is observed. The distribution of emitter energies reveals that most reside in two spectrally isolated bands, leaving a less populated intermediate band that is spectrally isolated from the ensembles. The spectral isolation is advantageous for high-purity quantum light emitters, and anti-bunched emission from one of these states is confirmed up to 25 K. Although the spatial distribution of strain is expected to influence the orientation of the transition dipoles of the emitters, multimodal emission polarization anisotropy and atomic force microscopy reveal that the macroscopic orientation of the wrinkles is not a good predictor of dipole orientation. Finally, the emission is found to change with thermal cycling from 4 to 290 K and back to 4 K, highlighting the need to control factors such as temperature-induced strain to enhance the robustness of this quantum emitter platform. The initial characterization here shows that controlled nanowrinkles of 1L-WSe2 generate quantum light in addition to uncovering potential challenges that need to be addressed for their adoption into quantum photonic technologies.

Investigating biochemical and structural changes of glycated collagen using multimodal multiphoton imaging, Raman spectroscopy, and atomic force microscopy

Advanced glycation end products (AGEs) form extracellular crosslinking with collagenous proteins, which contributes to the development of diabetic complications. In this study, AGEs-related pentosidine (PENT) crosslinks-induced structural and biochemical changes are studied using multimodal multiphoton imaging, Raman spectroscopy and atomic force microscopy (AFM). Decellularized equine pericardium (EP) was glycated with four ribose concentrations ranging between 5 and 200 mM and monitored for up to 30 days. Two-photon excited fluorescence (TPEF) and second harmonic generation (SHG) microscopic imaging probed elastin and collagen fibers, respectively. The glycated EP showed a decrease in the SHG intensities associated with loss of non-centrosymmetry of collagen and an increase of TPEF intensities associated with PENT crosslinks upon glycation. TPEF signals from elastin fibers were unaffected. A three-dimensional reconstruction with SHG + TPEF z-stack images visualized the distribution of collagen and elastin within the EP volume matrix. In addition, Raman spectroscopy (RS) detected changes in collagen-related bands and discriminated glycated from untreated EP. Furthermore, AFM scans showed that the roughness increases and the D-unit structure of fibers remained unchanged during glycation. The PENT crosslinked-induced changes are discussed in the context of previous studies of glutaraldehyde- and genipin-induced crosslinking and collagenase-induced digestion of collagen. We conclude that TPEF, SHG, RS, and AFM are effective, label-free, and non-destructive methods to investigate glycated tissues, differentiate crosslinking processes, and characterize general collagen-associated and disease-related changes, in particular by their RS fingerprints.

Towards understanding Shewanella algae-induced degradation of passive film of stainless steel based on electrochemical, XPS and multi-mode AFM analyses

The degradation of the passive film of stainless steel caused by Shewanella algae was investigated through electrochemical tests, X-ray photoelectron spectroscopy and atomic force microscopy (AFM). The dynamic mode and the nano manipulation mode of AFM were adopted to obtain the 3D topography of cell/passive film interfaces and to manipulate cell movement, respectively. The surface Volta potential scanning by tapping-amplitude modulation mode and the conductivity tests by PeakForce-TUNA mode of AFM revealed the electron injection phenomenon from S. algae cells into adjacent passive film, which promoted the reduction of Fe3+ compounds and accelerated the degradation of passive film.

A cantilever-based, ultrahigh-vacuum, low-temperature scanning probe instrument for multidimensional scanning force microscopy.

Cantilever-based atomic force microscopy (AFM) performed under ambient conditions has become an important tool to characterize new material systems as well as devices. Current instruments permit robust scanning over large areas, atomic-scale lateral resolution, and the characterization of various sample properties using multifrequency and multimodal AFM operation modes. Research of new quantum materials and devices, however, often requires low temperatures and ultrahigh vacuum (UHV) conditions and, more specifically, AFM instrumentation providing atomic resolution. For this, AFM instrumentation based on a tuning fork force sensor became increasingly popular. In comparison to microfabricated cantilevers, the more macroscopic tuning forks, however, lack sensitivity, which limits the measurement bandwidth. Moreover, multimodal and multifrequency techniques, such as those available in cantilever-based AFM carried out under ambient conditions, are challenging to implement. In this article, we describe a cantilever-based low-temperature UHV AFM setup that allows one to transfer the versatile AFM techniques developed for ambient conditions to UHV and low-temperature conditions. We demonstrate that such a cantilever-based AFM offers experimental flexibility by permitting multimodal or multifrequency operations with superior force derivative sensitivities and bandwidths. Our instrument has a sub-picometer gap stability and can simultaneously map not only vertical and lateral forces with atomic-scale resolution, but also perform rapid overview scans with the tip kept at larger tip–sample distances for robust imaging.

Single-cell level investigation of microbiologically induced degradation of passive film of stainless steel via FIB-SEM/TEM and multi-mode AFM

The degradation of passive films of a stainless steel by S. algae was investigated at the single-cell level. The focused ion beam-scanning/transmission electron microscopy showed that the passive film underneath the adherent S. algae cell was significantly thinner than that without bacterial coverage after 3 days of inoculation. Atomic force microscopy (AFM) in the nano manipulation mode was used to move the bacterial cell and AFM in the dynamic mode revealed the nanoscale corrosion pit underneath. Peak force tapping-frequency modulation mode of AFM showed high Volta potentials at the pit center and low Volta potentials around the bacterial cell.

Effect of air squeeze film damping in multi-mode atomic force microscopy

Effect of air squeeze film damping in multi-mode atomic force microscopy

Facile fabrication of 2D material multilayers and vdW heterostructures with multimodal microscopy and AFM characterization

Reliable transfer processes that enable manipulation of two-dimensional (2D) materials, e.g., transition metal dichalcogenides (TMDCs) and MXenes, from one substrate to another has been a necessity for successful device fabrication. With both mechanical exfoliation and chemical vapor deposition (CVD) widely used, a versatile, clean, deterministic, and yet simple transfer technique is highly needed. To address such need, we developed a transfer method that takes advantage of wettability contrast between interfaces without the use of sacrificial layers or chemical processes. More importantly, a setup was developed to carry out this transfer method with high sample selectivity and fine control of the position and orientation of transferred TMDC crystals, a feature required for fabrication of the devices based on vertical 2D heterostructures. Using both exfoliated and CVD grown materials and subsequent atomic force microscopy (AFM), photoluminescence (PL), confocal Raman and tip enhanced Raman spectroscopy (TERS) characterization, we ascertained the quality of interfaces resulting from the transfer process while preserving excellent 2D material integrity. PL and TERS maps revealed nanometer-scale heterogeneities in the interfaces of fabricated heterostructures, which should enable further perfection of the transfer technique. TERS/TEPL information were employed to identify areas suitable for nanodevice fabrication, making the reported transfer and characterization methods ideal for making high quality assembly of 2D heterostructure more accessible, which should facilitate exploration of vertical 2D heterostructures for applications in electronics, batteries, solar cells, and twistronics.

Anion conductive membrane performance facilitation via tethering flexible with rigid backbones using oscillational chain

Herein, a novel strategy to improve the performance of anion exchange membranes (AEMs) is adopted to build a crosslinked structure by tethering the rigid poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) backbone and the flexible poly(4-vinylphenol) (PVP) backbone using an oscillational chain. The incompatibility between the PPO and PVP backbones makes them self-aggregated resulting in occurrence of distinct microphase separation and development of ion transport channels in the AEMs to facilitate the transport of hydroxide ion. The microphase separation of the as-prepared AEMs has been revealed by transmission electron microscopy (TEM) and DI multimode atomic force microscopy (AFM). The existence of the hydrophilic PVP chain also ensures sufficient water uptake to enhance the conductivity of the AEMs. A maximum ionic conductivity of 134 mS cm−1 is achieved at 80 °C by the PPO-c-PVP-40% (40% is the molar content of PVP chains) membrane. A maximum power density of 173 mW cm−2 at 80 °C is obtained by a H2/O2 single cell using the PPO-c-PVP-40% membrane electrode assembly. The PPO-c-PVP-40% membrane also exhibits robust alkaline stability (retains about 90% ionic conductivity after 480 h alkaline stability test) and excellent mechanical property. Those render the AEMs a potential membrane electrode material for fuel cell applications.

High-energy 120 MeV Au9+ ion beam-induced modifications and evaluation of craters in surface morphology of SnO2 and TiO2 nanocomposite thin films

The electronic excitation and modification in the properties of the target material occur due to the kinetic energy loss of incident ions mainly through the inelastic collision with atomic electrons in the process of electronic energy stopping. Nanocomposite tin oxide (SnO2) and titanium dioxide (TiO2) thin film were grown on silicon and ITO substrates using RF magnetron-sputtering process. These thin films were irradiated by 120 MeV Au9+ Swift Heavy Ion (SHI) beam with varying fluence from 5 × 1011 ions cm−2 to 2 × 1013 ions cm−2 to induce modifications in thin films by dense electronic excitation. Surface morphology and depth profile of craters (approx. 85 nm) have been characterized by multimode atomic force microscopy (AFM). Grain mapping of AFM images provided the variation in grain size in the range of 72–279 nm and RMS roughness increased (4.01–23.6 nm) with increasing the ion fluence. Scanning Electron Microscopy (SEM) was also carried out to confirm the formation of craters in the irradiated film. X-ray diffraction (XRD) technique has been used for the structural analysis of virgin and irradiated thin films. XRD patterns established the formation of film in mixed (rutile and gamma) phase. Further, the crystallite size was evaluated using the Debye–Scherrer and Williamson–Hall method. It was found that crystallite size lie in the range of 36–54 nm which increased for the lower fluence and then decreased for higher fluence. The ion irradiation-induced strain has been explained by Thermal spike and Coulomb explosion model. UV–Vis study showed that the optical band gap reduced from 3.87 to 3.72 eV with increasing the ion fluence which can be ascribed to the formation of intermediate states and free radicals between the valance and band conduction band. Rutherford Backscattering Spectrometry (RBS) ensured that the film thickness decreased from 210 to 183 nm with increasing the ion fluence. The simulation of the RBS spectra provides the elemental composition of Sn (0.37), Ti (0.65) and O (0.85) in SnO2 and TiO2 nanocomposite thin films.

A case study of the electrical properties of astrocytes by multimode AFM.

Astrocytes play an important role in the physiological functions of the central nervous system. In this study, contact potential differences (CPD) and capacitance gradients of the cell bodies and glial filaments of astrocytes were measured. Charge propagation properties in the astrocyte gap junctions were also studied using multimode Atomic Force Microscopy (AFM) at nanometre resolution. The CPD of the cell bodies and glial filaments were 324.2 ± 138.4 and 119.1 ± 31.7 mV, respectively. The measured capacitance gradients were 1.51 ± 0.31 and 1.98 ± 0.32 zFnm-1 , respectively. The gap junctions in the astrocytes showed no charge propagation and were not electrically sensitive. This furthers our understanding of astrocytes and other types of neuroglia. LAY DESCRIPTION: Neuroglia cells play important structural and functional roles in central nervous system (CNS). Neuroglia cells exceed the number of neurons by 10∼50 and can be divided into macroglia and microglia. Astrocytes are macroglia and are the largest and most abundant cells in the CNS. Astrocytes lack axons and dendrites and do not propagate action potentials. They have few cytoplasmic organelles, but possess abundant glial filaments, the main components of the cytoskeleton. Glial filaments are composed of the glial fibrillary acidic protein (GFAP). Astrocytes produce intercellular calcium waves in their gap junctions mediated through receptor activator (such as glutamate) to permit signal transduction._ENREF_5 In addition to their role in the support and nutrition of neurons, astrocytes are involved in various types of CNS activity including: (1) cytokine secretion for neuronal survival, growth and differentiation; (2) protection from brain injury; (3) modulation of the blood brain barrier; and (4) neuronal immunity. Bidirectional crosstalk between the astrocytes and neurons exists. Astrocytes can be activated by neurotransmitters released and can themselves release gliotransmitters to act upon neurons. Astrocytes are closely related to various disease states, including epilepsy and Alzheimer's disease. In this study, the electrical properties of astrocytes, including the contact potential difference (CPD) and capacitance gradients of the cell bodies and glial filaments, and charge propagation in the gap junctions were investigated at the nanometer level using quantitative Kelvin Probe Force Microscopy (KPFM) and Electrostatic Force Microscopy (EFM). The CPD of the cell bodies and glial filaments of the astrocytes were 324.2 mV and 119.1 mV, respectively. Capacitance gradients of the cell bodies and glial filaments of the astrocytes were 1.51 zF/nm and 1.98 zF/nm, respectively. Gap junctions in the astrocytes do not perform charge propagation functions and the astrocytes are not electrically sensitive. One should note that these results from KPFM and EFM were measured on dried cell and the situation might be different when studying in operando environment, still these findings aid our understanding of the electrical properties and functions of astrocytes, and further our knowledge of the electrical properties of the CNS.

Identifying Nanoscale Structure-Function Relationships Using Multimodal Atomic Force Microscopy, Dimensionality Reduction, and Regression Techniques.

Correlating nanoscale chemical specificity with operational physics is a long-standing goal of functional scanning probe microscopy (SPM). We employ a data analytic approach combining multiple microscopy modes using compositional information in infrared vibrational excitation maps acquired via photoinduced force microscopy (PiFM) with electrical information from conductive atomic force microscopy. We study a model polymer blend comprising insulating poly(methyl methacrylate) (PMMA) and semiconducting poly(3-hexylthiophene) (P3HT). We show that PiFM spectra are different from FTIR spectra but can still be used to identify local composition. We use principal component analysis to extract statistically significant principal components and principal component regression to predict local current and identify local polymer composition. In doing so, we observe evidence of semiconducting P3HT within PMMA aggregates. These methods are generalizable to correlated SPM data and provide a meaningful technique for extracting complex compositional information that is impossible to measure from any one technique.

Graphene nanosheet/polyaniline composite for transparent hole transporting layer

Composites based on graphene and water-dispersible polyaniline-poly(2-acrylamido-2-methyl-1-propanesulfonic acid) complex were shown as materials promising for the development of hole transporting layers (HTLs). By using multimodal atomic force microscopy, transmission electron microscopy, cyclic voltammetry and conductivity measurements, the relationship between the oxidation degree of graphene and the morphology, electrical conductivity and electron energy structure of HTLs was revealed. Utilizing the HTLs in organic solar cells it was shown that graphene nanostacks, rather than oxidized graphene nanostacks, enhanced the performance of the cells by increasing the roughness of the HTL surface, which caused the improvement of the short circuit current.

Mechanical characteristics of FeAl2O4 and AlFe2O4 spinel phases in coatings – A study combining experimental evaluation and first-principles calculations

FeAl2O4 and AlFe2O4 have similar spinel structures but different atomic arrangements, leading to different properties. In this study, mechanical properties and structures of the two spinel phases in composite coatings prepared by reactive plasma spraying of Fe2O3-Al composite powder were investigated by means of multi-mode atomic force microscopy, X-ray diffraction, and scanning electron microscopy. It was demonstrated that AlFe2O4 was stronger than FeAl2O4 with a higher electron work function (EWF). First-principles calculations were conducted to understand the difference in mechanical properties between the two phases. It was shown that FeAl2O4 and AlFe2O4 have “normal” and “inverse” spinel structures with different configurations of valence electrons: Fe2+tet(Al3+)2O4 and Fe3+tet(Fe2+Al3+)octO4. Compared to Fe2+tet(Al3+)2O4, Fe3+tet(Fe2+Al3+)octO4 has its O and Fe atoms in the octahedral sites forming covalent bonds, which increase the stability and strength of the crystal, corresponding to higher EWF and larger bulk, shear and Young's moduli.

(Industrial Electrochemistry and Electrochemical Engineering Division Student Achievement Award) Engineering the Ionic Polymer Phase Surface Properties of a PEM Fuel Cell Catalyst Layer

During high power density operations, the performance of polymer electrolyte membrane fuel cells (PEMFCs) is limited by high water saturation levels in the cathode catalyst layer due to high wettability of the ionic polymer phase. A new heat treatment was used to create and permanently lock-in the surface structure of a biphasic membrane (Nafion® 212). Several surface characterization techniques were used to verify the engineered membrane’s surface after heat treatment, including contact angle, multi-mode atomic force microscopy (AFM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). We found that specific heat treatment conditions will lead to the formation of either a hydrophobic or hydrophilic surface layer. The results of this research will guide the design of a new class of PEMFC catalyst layers. Engineered PEMFC catalyst layers are expected to prevent electrode flooding, therefore leading to higher performance and efficiency during high power density operations.

High-frequency multimodal atomic force microscopy.

Multifrequency atomic force microscopy imaging has been recently demonstrated as a powerful technique for quickly obtaining information about the mechanical properties of a sample. Combining this development with recent gains in imaging speed through small cantilevers holds the promise of a convenient, high-speed method for obtaining nanoscale topography as well as mechanical properties. Nevertheless, instrument bandwidth limitations on cantilever excitation and readout have restricted the ability of multifrequency techniques to fully benefit from small cantilevers. We present an approach for cantilever excitation and deflection readout with a bandwidth of 20 MHz, enabling multifrequency techniques extended beyond 2 MHz for obtaining materials contrast in liquid and air, as well as soft imaging of delicate biological samples.

Determining surface properties with bimodal and multimodal AFM

Conventional dynamic atomic force microscopy (AFM) can be extended to bimodal and multimodal AFM in which the cantilever is simultaneously excited at two or more resonance frequencies. Such excitation schemes result in one additional amplitude and phase images for each driven resonance, and potentially convey more information about the surface under investigation. Here we present a theoretical basis for using this information to approximate the parameters of a tip-surface interaction model. The theory is verified by simulations with added noise corresponding to room-temperature measurements.

Energy transfer between eigenmodes in multimodal atomic force microscopy

We present experimental and computational investigations of tetramodal and pentamodal atomic force microscopy (AFM), respectively, whereby the first four or five flexural eigenmodes of the cantilever are simultaneously excited externally. This leads to six to eight additional observables in the form of amplitude and phase signals, with respect to the monomodal amplitude modulation method. We convert these additional observables into three or four dissipation and virial expressions, and show that these quantities can provide enhanced contrast that would otherwise remain hidden in the original observables. We also show that the complexity of the multimodal impact leads to significant energy transfer between the active eigenmodes, such that the dissipated power for individual eigenmodes may be positive or negative, while the total dissipated power remains positive. These results suggest that the contrast of individual eigenmodes in multifrequency AFM should be not be considered in isolation and that it may be possible to use different eigenfrequencies to probe sample properties that respond to different relaxation times.

Multi-frequency tapping-mode atomic force microscopy beyond three eigenmodes in ambient air.

We present an exploratory study of multimodal tapping-mode atomic force microscopy driving more than three cantilever eigenmodes. We present tetramodal (4-eigenmode) imaging experiments conducted on a thin polytetrafluoroethylene (PTFE) film and computational simulations of pentamodal (5-eigenmode) cantilever dynamics and spectroscopy, focusing on the case of large amplitude ratios between the fundamental eigenmode and the higher eigenmodes. We discuss the dynamic complexities of the tip response in time and frequency space, as well as the average amplitude and phase response. We also illustrate typical images and spectroscopy curves and provide a very brief description of the observed contrast. Overall, our findings are promising in that they help to open the door to increasing sophistication and greater versatility in multi-frequency AFM through the incorporation of a larger number of driven eigenmodes, and in highlighting specific future research opportunities.

Energy dissipation in multifrequency atomic force microscopy.

The instantaneous displacement, velocity and acceleration of a cantilever tip impacting onto a graphite surface are reconstructed. The total dissipated energy and the dissipated energy per cycle of each excited flexural mode during the tip interaction is retrieved. The tip dynamics evolution is studied by wavelet analysis techniques that have general relevance for multi-mode atomic force microscopy, in a regime where few cantilever oscillation cycles characterize the tip–sample interaction.