Scanning Probe Microscopy Approach Research Articles

Enabling focused ion beam sample preparation for application in reverse tip sample scanning probe microscopy

Focused ion beam (FIB) has become a powerful tool for transmission electron microscopy sample preparation in the nanoelectronics industry and has in recent years also shown its benefits for specific preparation steps in electrical scanning probe microscopy (SPM). Most recently, a novel SPM approach – so-called reverse tip sample (RTS) SPM – has been proposed in which the position of sample and tip are switched compared to standard SPM; in RTS SPM the sample is attached to the end of a cantilever beam. To achieve this configuration, the region of interest must first be extracted from a substrate and then needs to be reliably fixed to the cantilever by FIB. Therefore, we have explored and developed dedicated FIB preparation methods for RTS SPM in this work. Our established procedures ensure a strong mechanical and good electrical connection of the sample to the cantilever for both cross-section and top view sample preparation. Furthermore, we introduce an approach for mounting samples from a full wafer size workflow. This paper presents the developed FIB procedures and discusses the quality and stability of all mounted samples and their electrical evaluation in RTS SPM.

Scanning Probe Microscopy Techniques for Studying the Cell Glycocalyx.

The glycocalyx is a brush-like layer that covers the surfaces of the membranes of most cell types. It consists of a mixture of carbohydrates, mainly glycoproteins and proteoglycans. Due to its structure and sensitivity to environmental conditions, it represents a complicated object to investigate. Here, we review studies of the glycocalyx conducted using scanning probe microscopy approaches. This includes imaging techniques as well as the measurement of nanomechanical properties. The nanomechanics of the glycocalyx is particularly important since it is widely present on the surfaces of mechanosensitive cells such as endothelial cells. An overview of problems with the interpretation of indirect data via the use of analytical models is presented. Special insight is given into changes in glycocalyx properties during pathological processes. The biological background and alternative research methods are briefly covered.

Correlating Structural and Electrical Characteristics of Threading Dislocations in GaN -on- Si Heterostructures and p - n Diodes by Multiple Microscopy Techniques

Structural and electrical properties of a- and a + c-type threading dislocations in metal-organic vapor-phase epitaxy-grown $\mathrm{Si}$-doped $\mathrm{Ga}\mathrm{N}$ (0001) are determined by combining multiple scanning probe microscopy approaches. The analysis examines the space-charge region (SCR) formed around dislocation cores and clarifies the role it plays in influencing the local recombination, the surface-potential characteristic, and even the conductivity. Direct evidence of the SCR is obtained from a differential capacitance (dC/dV) measurement at dislocation sites on the (0001) surface. Experimental dC/dV (V) measurement results supported by technology computer-aided design calculations of capacitance, accounting for the theoretical deep levels related to different atom-core structures of the identified dislocations, reveal quantitative differences in their respective trap densities. This study is extended to p-n $\mathrm{Ga}\mathrm{N}$ vertical diodes to analyze the doping distribution across active layers. Through a correlated cross-section investigation combining electron-channeling contrast-imaging microscopy, the underlying dislocations within the depth limited by the screening of their SCRs are found to severely impact the homogeneity of the cross-section dC/dV contrast in the low-doped n-type drift layer of the diodes. This raises serious concerns regarding any quantification efforts by differential capacitance measurements in $\mathrm{Ga}\mathrm{N}$ on $\mathrm{Si}$, where the dislocation density is in the order of ${10}^{9}\phantom{\rule{0.2em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}2}$.

Envision and Appraisal of Biomolecules and Their Interactions through Scanning Probe Microscopy

Scanning probe microscopy (SPM) has gifted a novel eye to envision nanotechnology and nanoscience. The SPM technique involves a sharp probe that moves over the sample surface and leads to produce signals, which facilitates a deep understanding of the structural, electronic, vibrational, optical, magnetic, (bio) chemical, and mechanical properties of the material. Scanning tunneling microscopy (STM) and atomic force microscopy (AFM) measure various kinds of physical properties such as electric current, force, and capacitance. Moreover, AFM shows a prominent feature over STM that it accepts insulating surfaces and can work under physiological conditions, making it feasible to study biological molecules. Herein, the SPM approach toward biomolecule imaging and appraising different physiological processes with molecular resolution is highlighted. The review raises awareness regarding current obstacles in biological sample preparation and possible ways to conquer these difficulties. Subsequently, the recent applications of STM and AFM on various biomolecules with representative examples like DNA, protein, and carbohydrates are discussed. The conductance measurement studies of the biological samples emphasize applications like drug delivery, biosensors, molecular electronics, and spintronics fields. This is followed by an outlook of future perspectives making a pavement toward the basic science and applied field of biomolecules using SPM technology.

Probing Temperature‐Induced Phase Transitions at Individual Ferroelectric Domain Walls

AbstractFerroelectric domain walls have emerged as one of the most fascinating objects in condensed matter physics due to the broad variability of functional behaviors they exhibit. However, the vast majority of domain walls studies have been focused on bias‐induced dynamics and transport behaviors. Here, the scanning probe microscopy approach based on piezoresponse force microscopy (PFM) with a dynamically heated probe, combining local heating and local biasing of the material is introduced. This approach is used to explore the thermal polarization dynamics in soft Sn2P2S6 ferroelectrics, and allows for the exploration of phase transitions at individual domain walls. The strong and weak modulation regimes for the thermal PFM are introduced. The future potential applications of heated probe approach for functional SPM measurements including piezoelectric, elastic, microwave, and transport measurements are discussed.

Simultaneous mapping of nanoscale dielectric, electrochemical, and ferroelectric surface properties of van der Waals layered ferroelectric via advanced SPM

Ferroelectric surfaces involve a complex interplay between polarization and dielectric properties, internal and external surface charge screening, and ionic and electrochemical effects. There is currently no good way to simultaneously capture all the required information at appropriate length scales. To this end, we present an advanced scanning probe microscopy approach for simultaneously mapping surface potential, dielectric, and piezoelectric properties on the nanoscale. For quantitatively mapping electromechancial properties, we utilize interferometric displacement sensing piezoresponse force microscopy, which measures the effective piezoelectric coefficient free of background artifacts such as the cantilever body electrostatics. The dielectric and surface electrochemical properties are captured during G-mode electrostatic force microscopy/Kelvin probe force microscopy operated in the lift mode. We show the capabilities of this approach on the chemically phase separated composite sample consisting of a van der Waals layered ferroelectric CuInP2S6 phase and a non-polar In4/3P2S6 phase. Finally, we demonstrate domain structure evolution during thermally stimulated phase transition.

Three-Dimensional Mapping of Resistivity and Microstructure of Composite Electrodes for Lithium-Ion Batteries.

Nanoparticle silicon-graphite composite electrodes are a viable way to advance the cycle life and energy density of lithium-ion batteries. However, characterization of composite electrode architectures is complicated by the heterogeneous mixture of electrode components and nanoscale diameter of particles, which falls beneath the lateral and depth resolution of most laboratory-based instruments. In this work, we report an original laboratory-based scanning probe microscopy approach to investigate composite electrode microstructures with nanometer-scale resolution via contrast in the electronic properties of electrode components. Applying this technique to silicon-based composite anodes demonstrates that graphite, SiOx nanoparticles, carbon black, and LiPAA binder are all readily distinguished by their intrinsic electronic properties, with measured electronic resistivity closely matching their known material properties. Resolution is demonstrated by identification of individual nanoparticles as small as ∼20 nm. This technique presents future utility in multiscale characterization to better understand particle dispersion, localized lithiation, and degradation processes in composite electrodes for lithium-ion batteries.

Investigation of Local Conduction Mechanisms in Ca and Ti-Doped BiFeO3 Using Scanning Probe Microscopy Approach.

In this work we demonstrate the role of grain boundaries and domain walls in the local transport properties of n- and p-doped bismuth ferrites, including the influence of these singularities on the space charge imbalance of the energy band structure. This is mainly due to the charge accumulation at domain walls, which is recognized as the main mechanism responsible for the electrical conductivity in polar thin films and single crystals, while there is an obvious gap in the understanding of the precise mechanism of conductivity in ferroelectric ceramics. The conductivity of the Bi0.95Ca0.05Fe1−xTixO3−δ (x = 0, 0.05, 0.1; δ = (0.05 − x)/2) samples was studied using a scanning probe microscopy approach at the nanoscale level as a function of bias voltage and chemical composition. The obtained results reveal a distinct correlation between electrical properties and the type of charged defects when the anion-deficient (x = 0) compound exhibits a three order of magnitude increase in conductivity as compared with the charge-balanced (x = 0.05) and cation-deficient (x = 0.1) samples, which is well described within the band diagram representation. The data provide an approach to control the transport properties of multiferroic bismuth ferrites through aliovalent chemical substitution.

Characterizing Individual Protein Aggregates by Infrared Nanospectroscopy and Atomic Force Microscopy.

The phenomenon of protein misfolding and aggregation results in the formation of highly heterogeneous protein aggregates, which are associated with neurodegenerative conditions such as Alzheimer's and Parkinson's diseases. In particular low molecular weight aggregates, amyloid oligomers, have been shown to possess generic cytotoxic properties and are implicated as neurotoxins in many forms of dementia. We illustrate the use of methods based on atomic force microscopy (AFM) to address the challenging task of characterizing the morphological, structural and chemical properties of these aggregates, which are difficult to study using conventional structural methods or bulk biophysical methods because of their heterogeneity and transient nature. Scanning probe microscopy approaches are now capable of investigating the morphology of amyloid aggregates with sub-nanometer resolution. We show here that infrared (IR) nanospectroscopy (AFM-IR), which simultaneously exploits the high resolution of AFM and the chemical recognition power of IR spectroscopy, can go further and enable the characterization of the structural properties of individual protein aggregates, and thus offer insights into the aggregation mechanisms. Since the approach that we describe can be applied also to the investigations of the interactions of protein assemblies with small molecules and antibodies, it can deliver fundamental information to develop new therapeutic compounds to diagnose or treat neurodegenerative disorders.

Correlative Confocal Raman and Scanning Probe Microscopy in the Ionically Active Particles of LiMn2O4 Cathodes.

In this contribution, a correlative confocal Raman and scanning probe microscopy approach was implemented to find a relation between the composition, lithiation state, and functional electrochemical response in individual micro-scale particles of a LiMn2O4 spinel in a commercial Li battery cathode. Electrochemical strain microscopy (ESM) was implemented both at a low-frequency (3.5 kHz) and in a high-frequency range of excitation (above 400 kHz). It was shown that the high-frequency ESM has a significant cross-talk with topography due to a tip-sample electrostatic interaction, while the low-frequency ESM yields a response correlated with distributions of Li ions and electrochemically inactive phases revealed by the confocal Raman microscopy. Parasitic contributions into the electromechanical response from the local Joule heating and flexoelectric effect were considered as well and found to be negligible. It was concluded that the low-frequency ESM response directly corresponds to the confocal Raman microscopy data. The analysis implemented in this work is an important step towards the quantitative measurement of diffusion coefficients and ion concentration via strain-based scanning probe microscopy methods in a wide range of ionically active materials.

Multifunctional atomic force probes for Mn2+ doped perovskite solar cells

Doping in organic–inorganic perovskite semiconductors is an effective method to tailor their optoelectronic properties. In this work, manganese-doped perovskite films with different Mn/Pb ratios ranging from 0% to 2% were systematically studied. The device performance of 0.2% Mn-doped devices was improved compared to that of a device without Mn. However, a further increase of the doping concentration induced a decrease in performance. Several characteristics (especially different scanning probe microscopy characteristics) reveal that an increased dopant concentration results in reduced crystallinity and a change in the film morphology and causes a deterioration in photovoltaic performance for higher dopant concentrations. In the best-performing samples (0.2%), a shift in the valence band level and band gap are found which are responsible for the increased open circuit voltage, while increased grain boundaries and lower surface charge density are responsible for a small reduction in the short circuit current. Thus, multifunctional scanning probe microscopy approaches, combined with different film characterization techniques, offer us effective tools to investigate the impact of doping in the perovskite materials and the corresponding device performance.

Electrochemomechanics with flexoelectricity and modelling of electrochemical strain microscopy in mixed ionic-electronic conductors

Recently, a new scanning probe microscopy approach, referred to as electrochemical strain microscopy (ESM), for probing local ionic flows and electrochemical reactions in solids based on the bias-strain coupling was proposed by Morozovska et al. Then, a series of theoretical papers for analyzing the image formation and spectroscopic mechanism of ESM were published within the framework of Fermi-Dirac statistics, the Vegard law, the direct flexoelectric coupling effect, the electrostriction effect, and so on. However, most of the models in these papers are limited to the partial coupling or particular process, and numerically solved by using decoupling approximation. In this paper, to model the ESM measurement with the coupling electrical-chemical-mechanical process, the chemical Gibbs function variational principle for the thermal electrical chemical mechanical fully coupling problem is proposed. The fully coupling governing equations are derived from the variational principle. When the tip concentrates the electric field within a small volume of the material, the inhomogeneous electric field is induced. So, both direct and inverse flexoelectric effects should be taken into account. Here, the bulk defect electrochemical reactions are also taken into account, which are usually omitted in the existing works. This theory can be used to deal with coupling problems in solids, including conductors, semiconductors, and piezoelectric and non-piezoelectric dielectrics. As an application of this work, a developed initial-boundary value problem is solved numerically in a mixed ion-electronic conductor. Numerical results show that it is meaningful and necessary to consider the bulk defect chemical reaction. Besides, the chemical reaction and the flexoelectric effect have an interactive influence on each other. This work can provide theoretical basis for the ESM as well as investigating the bulk chemical reaction process in solids.

Solid-state electrochemistry on the nanometer and atomic scales: the scanning probe microscopy approach.

Energy technologies of the 21(st) century require an understanding and precise control over ion transport and electrochemistry at all length scales - from single atoms to macroscopic devices. This short review provides a summary of recent studies dedicated to methods of advanced scanning probe microscopy for probing electrochemical transformations in solids at the meso-, nano- and atomic scales. The discussion presents the advantages and limitations of several techniques and a wealth of examples highlighting peculiarities of nanoscale electrochemistry.

Open-loop band excitation Kelvin probe force microscopy

A multidimensional scanning probe microscopy approach for quantitative, cross-talk free mapping of surface electrostatic properties is demonstrated. Open-loop band excitation Kelvin probe force microscopy (OL BE KPFM) probes the full response-frequency-potential surface at each pixel at standard imaging rates. The subsequent analysis reconstructs work function, tip–surface capacitance gradient and resonant frequency maps, obviating feedback-related artifacts. OL BE KPFM imaging is demonstrated for several materials systems with topographic, potential and combined contrast. This approach combines the features of both frequency and amplitude KPFM and allows complete decoupling of topographic and voltage contributions to the KPFM signal.

Magnetic Imaging on the Nanometer Scale Using Low-Temperature Scanning Probe Techniques

Multiple techniques now exist for the investigation of nanoscale magnetic properties, extending from Lorentz microscopy and magneto-optical imaging (MOKE) to scanning probe microscopy approaches (see Figure 1 for an overview). Among the latter, the most widely used techniques offering both high spatial and high magnetic-field resolution are magnetic force microscopy (MFM) and scanning Hall probe microscopy (SHPM). Both techniques are well known for their versatility and ease of use and can be further adapted for operation in cryogenic conditions. This property is crucial for all areas of research where high magnetic fields are required and where the influence of thermal energy/broadening needs to be suppressed. For example, much of today's fundamental research on superconductivity, spintronics, and magnetic data storage is taking place at low temperatures.

Mapping Irreversible Electrochemical Processes on the Nanoscale: Ionic Phenomena in Li Ion Conductive Glass Ceramics

A scanning probe microscopy approach for mapping local irreversible electrochemical processes based on detection of bias-induced frequency shifts of cantilevers in contact with the electrochemically active surface is demonstrated. Using Li ion conductive glass ceramic as a model, we demonstrate near unity transference numbers for ionic transport and establish detection limits for current-based and strain-based detection. The tip-induced electrochemical process is shown to be a first-order transformation and nucleation potential is close to the Li-metal reduction potential. Spatial variability of the nucleation bias is explored and linked to the local phase composition. These studies both provide insight into nanoscale ionic phenomena in practical Li-ion electrolyte and also open pathways for probing irreversible electrochemical, bias-induced, and thermal transformations in nanoscale systems.

Decoupling Electrochemical Reaction and Diffusion Processes in Ionically-Conductive Solids on the Nanometer Scale

We have developed a scanning probe microscopy approach to explore voltage-controlled ion dynamics in ionically conductive solids and decouple transport and local electrochemical reactivity on the nanometer scale. Electrochemical strain microscopy allows detection of bias-induced ionic motion through the dynamic (0.1-1 MHz) local strain. Spectroscopic modes based on low-frequency (∼1 Hz) voltage sweeps allow local ion dynamics to be probed locally. The bias dependence of the hysteretic strain response accessed through first-order reversal curve (FORC) measurements demonstrates that the process is activated at a certain critical voltage and is linear above this voltage everywhere on the surface. This suggests that FORC spectroscopic ESM data separates local electrochemical reaction and transport processes. The relevant parameters such as critical voltage and effective mobility can be extracted for each location and correlated with the microstructure. The evolution of these behaviors with the charging of the amorphous Si anode in a thin-film Li-ion battery is explored. A broad applicability of this method to other ionically conductive systems is predicted.

Nanoscale investigation of the structural and chemical changes induced by oxidation on carbon black surfaces: A scanning probe microscopy approach

Scanning tunneling microscopy (STM) and noncontact tapping mode atomic force microscopy (AFM) have been employed to study on a local scale the structural and, for the first time, the chemical changes of carbon black (CB) particles following plasma oxidation. STM imaging of the pristine, untreated particles revealed a relatively ordered structure of tiny crystallites with a few amorphous regions. After plasma treatment, the crystallites were no longer observed and the CB particle surface exhibited a noticeable and ubiquitous increase in atomic-scale disorder. Phase contrast images obtained with noncontact tapping mode AFM indicated that the untreated CB particles were essentially hydrophobic as a pristine basal surface of graphite, but with occasional hydrophilic patches. By contrast, their plasma-treated counterparts displayed enhanced hydrophilicity as a result of the introduction of oxygen onto the CB surface, the presence of which was evidenced by X-ray photoelectron spectroscopy, but most significantly, such enhancement was observed to be quite uniform at a local scale of individual particles. The possibility of investigating on a very local scale the chemical behavior of oxidized CB particles should be useful for the control and optimization of their dispersion properties in different systems.

Scanning Probe Microscopy in Catalysis

This review discusses the recent progress in the application of scanning probe microscopy (SPM) in catalysis. SPM proves to be an invaluable technique for imaging catalytic surfaces and interfaces. Most SPM research is related to the structural and morphological transformation associated with catalyst preparation and use. Real-time SPM observation of surface dynamics including adsorption, diffusion and reaction, provides invaluable insights to the mechanism of catalysis. SPM is also used to shape and manipulate surfaces and surface processes. Fabrication of nanostructured catalysts, direct manipulation of adsorbed atoms and molecules and tip-mediated reactions are some examples of new SPM approach in catalyst research.