Conductive Atomic Force Microscopy Research Articles

Domains with Varying Conductance in Tensile Strained SrMnO3 Thin Films Using Out‐of‐Plane Electric Fields

AbstractDomains and domain wall engineering have been extensively explored in ferroic materials for a wide range of applications in nanoelectronics and spintronics. Complex oxides exhibiting strongly correlated properties are model platforms for such studies where response to strain or external stimuli such as electric field, temperature and light can be probed. Here, domains in strained SrMnO3 films, grown on a degenerate semiconductor, allowing for conduction in an out‐of‐plane geometry, are studied using a combination of microscopy probes. Using conductive atomic force microscopy, electrically isolated domains with varying conductance are found and their temporal evolution is investigated. Further, their formation and microstructure are studied using scanning transmission electron microscopy and secondary electron contrast in scanning electron microscopy. An important contribution is establishing that the observed domains are formed by cracks, driven by inhomogeneous strain relaxation throughout the film, resulting in significantly high strain planes. The potential of secondary electrons to detect domain dependent contrast over a large area, ensuing due to the use of a degenerate semiconductor correlates with the conductive properties of the domains and serves as a new direction to probe domains and domain walls in ferroic materials.

Fabrication of Electronically Conductive Protein-Heme Nanowires for Power Harvesting.

Electronically conductive protein-based materials can enable the creation of bioelectronic components and devices from sustainable and nontoxic materials, while also being well-suited to interface with biological systems, such as living cells, for biosensor applications. However, as proteins are generally electrical insulators, the ability to render protein assemblies electroactive in a tailorable manner can usher in a plethora of useful materials. Here, an approach to fabricate electronically conductive protein nanowires is presented by aligning heme molecules in proximity along protein filaments, with these nanowires also possessing charge transfer abilities that enable energy harvesting from ambient humidity. The heme-incorporated protein nanowires demonstrate electron transfer over micrometer distances, with conductive atomic force microscopy showing individual nanowires having comparable conductance to other previously characterized heme-based bacterial nanowires. Exposure of multilayer nanowire films to humidity produces an electrical current, presumably through water molecules ionizing carboxyl groups in the filament and creating an unbalanced total charge distribution that is enhanced by the heme. Incorporation of heme and potentially other metal-center porphyrin molecules into protein nanostructures could pave the way for structurally- and electrically-defined protein-based bioelectronic devices.

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.

Photoswitchable optoelectronic properties of 2D MoSe2/diarylethene hybrid structures

The ability to modulate optical and electrical properties of two-dimensional (2D) semiconductors has sparked considerable interest in transition metal dichalcogenides (TMDs). Herein, we introduce a facile strategy for modulating optoelectronic properties of monolayer MoSe2 with external light. Photochromic diarylethene (DAE) molecules formed a 2-nm-thick uniform layer on MoSe2, switching between its closed- and open-form isomers under UV and visible irradiation, respectively. We have discovered that the closed DAE conformation under UV has its lowest unoccupied molecular orbital energy level lower than the conduction band minimum of MoSe2, which facilitates photoinduced charge separation at the hybrid interface and quenches photoluminescence (PL) from monolayer flakes. In contrast, open isomers under visible light prevent photoexcited electron transfer from MoSe2 to DAE, thus retaining PL emission properties. Alternating UV and visible light repeatedly show a dynamic modulation of optoelectronic signatures of MoSe2. Conductive atomic force microscopy and Kelvin probe force microscopy also reveal an increase in conductivity and work function of MoSe2/DAE with photoswitched closed-form DAE. These results may open new opportunities for designing new phototransistors and other 2D optoelectronic devices.

Spreading resistance and conductance anisotropy in multilayer MoS2

The increasing interest in realizing the full potential of two-dimensional (2D) layered materials for developing electronic components strongly relies on quantitative understanding of their anisotropic electronic properties. Herein, we use conductive atomic force microscopy to study the anisotropic electrical conductance of multilayer MoS2 by measuring the spreading resistance of circular structures of different radii ranging from 150 to 400 nm. The observed inverse scaling of the spreading resistance with contact radius, with an effective resistivity of ρeff  = 2.89 Ω cm, is compatible with a diffusive transport model. A successive etch of the MoS2 nanofilms was used to directly measure the out-of-plane resistivity, i.e., 29.43 ± 7.78 Ω cm. Based on the scaling theory for conduction in anisotropic materials, the model yields an in-plane resistivity of 0.28 ± 0.07 Ω cm and an anisotropy of ∼100 for the ratio between the in-plane and out-of-plane resistivities. The obtained anisotropy indicates that the probed surface area can extend up to 400 times the metal contact area, whereas the penetration depth is limited to roughly 20% of the contact radius. Hence, for contact radius less than 3 nm, the conduction will be limited to the surface. Our investigation offers important insight into the anisotropic transport behavior of MoS2, a pivotal factor enabling the design optimization of miniaturized devices based on 2D materials.

Optically Tunable Electrical Oscillations in Oxide-Based Memristors for Neuromorphic Computing.

The application of hardware-based neural networks can be enhanced by integrating sensory neurons and synapses that enable direct input from external stimuli. Here, we report direct optical control of an oscillatory neuron based on volatile threshold switching in V3O5. The devices exhibit electroforming-free operation with switching parameters that can be tuned by optical illumination. Using temperature-dependent electrical measurements, conductive atomic force microscopy (C-AFM), in-situ thermal imaging, and lumped element modelling, we show that the changes in switching parameters, including threshold and hold voltages, arise from overall conductivity increase of the oxide film due to the contribution of both photo-conductive and bolometric characteristics of V3O5, which eventually affects the oscillation dynamics. Furthermore, our investigation reveals V3O5 as a new bolometric material with a remarkable temperature coefficient of resistivity (TCR) as high as -4.6% K-1 at 423 K. We show the utility of optically tuneable device response and spiking frequency by demonstrating in-sensor reservoir computing with reduced computational effort and an optical encoding layer for spiking neural network, respectively, using a simulated array of devices. This article is protected by copyright. All rights reserved.

Tailored Band Alignment for Improved Carrier Transport in Composition-Controlled Sb2(S,Se)3.

Sb2(S,Se)3 is a highly available energy material with a tunable bandgap by adjusting the S/Se ratio. Increasing the Se ratio can enhance the efficiency of Sb2(S,Se)3 solar cells, with a higher short-circuit current (JSC). However, the accompanying decrease in the open-circuit voltage (VOC) restricts further improvement. The defect passivation is important, since it can reduce carrier recombination, enhancing the VOC. In this study, the relevance of the S/Se ratio, defect concentration, and VOC was investigated. The samples with or without the deposition of Se-rich Sb2(S,Se)3 onto S-rich Sb2(S,Se)3 were used for defect characterization. Different surface compositions were confirmed by Raman spectroscopy. The complicated subdefect states of S-rich Sb2(S,Se)3 were shown through photoluminescence and conductive atomic force microscopy, and a decrease in the defect concentration was observed through surface photovoltage. The improvement of JSC via bandgap grading and the simultaneous VOC improvement by defect passivation resulted in efficient cell performance.

Nanoelectrical monitoring the nonvolatile behavior of VO2 under multi-field stimulate by conductive atomic force microscopy

The ability to control the metal–insulator phase transition is crucial for future neuromorphic and memristive technologies. The key goal of this implementation is to understand and control the nanoscale mechanisms that support these two fundamental switching modalities (volatile and non-volatile states). Here, by adjusting the temperature (60 °C) close to the metal–insulator transition temperature, external application of low voltage (1 V) and laser excitation (18.6 mw · cm−2) can complete the metal–insulator transition of vanadium dioxide (VO2). The nonvolatile behavior of the VO2 devices was nanoelectrically monitored using conductive atomic force microscopy (C-AFM). Using this technique, we were able to reversibly transform the local switching response from volatile to nonvolatile, providing a unique approach for nanoelectrical monitoring in phase transition materials.

Evaluating the optoelectronic properties of individual CsPbBr3 microcrystals by electric AFM techniques

All-inorganic perovskite materials are attracting the attention of researchers owing to the good performance that they exhibit in optoelectronic device applications. In particular, cesium lead halide single crystals are of interest for their electric conductivity. However, the conductive properties of these materials are still far from being fully understood. In this work, we used several scanning probe microscopy techniques to investigate different properties of CsPbBr3 single crystals, namely their topography, electric conductivity, electric surface potential and ferroelectricity. We observed heterogeneity in conductance and work function of the different facets by using conductive atomic force microscopy and Kelvin probe force microscopy measurements. Additionally, piezo-response force microscopy was carried out to gain insight on the origin of the hysteresis in our microcrystals. Our results show the absence of ferroelectric domains and we attribute the I–V hysteresis to ionic migration within the crystal.

Conducting atomic force microscopy studies on domain wall currents of Bi5 Ti3 FeO15 nanodots fabricated by anodic aluminum oxide nanotemplate and sol-gel process.

We investigated the local current characteristics of Bi5 Ti3 FeO15 (BTFO) nanodots on Nb-doped SrTiO3 substrates affected by their ferroelectric domain structures and domain walls. The BTFO nanodots with a diameter of about 50 nm were fabricated by anodic aluminum oxide nanotemplates and a BTFO sol-gel process. Based on a piezoresponse force microscope, it was confirmed that domain walls were formed in the ferroelectric domain structures of the epitaxial BTFO nanodots. Current changes due to ferroelectric tunneling junctions according to ferroelectric polarizations in epitaxial BTFO nanodots were confirmed by conduction atomic force microscopy. In particular, the domain walls formed in the epitaxial BTFO nanodots formed high currents compared to the currents in ferroelectric tunneling junctions due to polarizations. RESEARCH HIGHLIGHTS: Ferroelectric Bi5 Ti3 FeO15 nanodots with a diameter of 50 nm. Ferroelectric domain structures observed with piezoresponse force microscopy. High domain wall currents observed at domain boundaries observed with conducting atomic force microscopy.

Covalent Organic Frameworks with Tunable Chirality for Chiral-Induced Spin Selectivity.

Chiral covalent organic frameworks (CCOFs) have attracted extensive interest for their potential applications in various enantioselective processes. However, the exploitation of chirality-induced spin selectivity (CISS) that enables a new technology for the injection of spin polarized current without the need for a permanent magnetic layer within CCOFs remains a largely untapped area of research. Here, we demonstrate that, for the first time, COFs can be an attractive platform to develop spin filter materials with efficient CISS. This facilitates the design and synthesis of a new family of Zn(salen)-based 2D CCOFs, namely, CCOFs-9-12, by imine condensation of chiral 1,2-diaminocyclohexane and tri- or tetra(salicylaldehyde) derivatives. CCOF-9, distinguished by its unique C2 symmetric "armchair" tetrasubstituted pyrene conformation, exhibits the most pronounced chirality among these materials and serves as a solid-state host, enabling the enantioselective adsorption of racemic drugs with an enantiomeric excess (ee) of up to 97%. After substituting diamagnetic zinc(II) ions for paramagnetic cobalt(II), the resulting CCOF-9-Co not only retains its high crystallinity, porosity, and exceptional chirality but also exhibits enhanced conductivity, a crucial factor for the effective observation of CISS. Magnetic conductive atomic force microscopy showed that CCOF-9-Co exhibited a remarkable CISS effect with up to an 88-94% spin polarization ratio. This phenomenon is further confirmed by the increased intensity in the magnetic circular dichroism (MCD) when CCOF-9-Co is under an external magnetic field. This work therefore shows the tremendous potential of CCOFs for controlling spin selectivity and will stimulate the creation of new types of crystalline polymers with strong CISS effects for spin filters.

A nanoscale study of hafnium oxide resistive memory switching dynamics

This paper deals with the set and reset time measurements of a resistive memory consisting of a Ti/TiN/HfO2 layer stack contacted with the tip of a conductive atomic force microscope in ultra high vacuum. We present measurements of the set and reset switching times in voltage pulse regime for different voltages and compliance currents. The experimental results are well reproduced by simulation. We derive analytical expressions for the set and reset times as function of experimental conditions. The effect of voltage and current on reset and set switching times is then discussed with the help of their analytical expressions, which are also applied on standard devices characteristics.

Atomic Defect Quantification by Lateral Force Microscopy.

Atomic defects in two-dimensional (2D) materials impact electronic and optoelectronic properties, such as doping and single photon emission. An understanding of defect-property relationships is essential for optimizing material performance. However, progress in understanding these critical relationships is hindered by a lack of straightforward approaches for accurate, precise, and reliable defect quantification on the nanoscale, especially for insulating materials. Here, we demonstrate that lateral force microscopy (LFM), a mechanical technique, can observe atomic defects in semiconducting and insulating 2D materials under ambient conditions. We first improve the sensitivity of LFM through consideration of cantilever mechanics. With the improved sensitivity, we use LFM to locate atomic-scale point defects on the surface of bulk MoSe2. By directly comparing LFM and conductive atomic force microscopy (CAFM) measurements on bulk MoSe2, we demonstrate that point defects observed with LFM are atomic defects in the crystal. As a mechanical technique, LFM does not require a conductive pathway, which allows defect characterization on insulating materials, such as hexagonal boron nitride (hBN). We demonstrate the ability to observe intrinsic defects in hBN and defects introduced by annealing. Our demonstration of LFM as a mechanical defect characterization technique applicable to both conductive and insulating 2D materials will enable routine defect-property determination and accelerate materials research.

Stripe noise removal in conductive atomic force microscopy

Conductive atomic force microscopy (c-AFM) can provide simultaneous maps of the topography and electrical current flow through materials with high spatial resolution and it is playing an increasingly important role in the characterization of novel materials that are being investigated for novel memory devices. However, noise in the form of stripe features often appear in c-AFM images, challenging the quantitative analysis of conduction or topographical information. To remove stripe noise without losing interesting information, as many as sixteen destriping methods are investigated in this paper, including three additional models that we propose based on the stripes characteristics, and thirteen state-of-the-art destriping methods. We have also designed a gradient stripe noise model and obtained a ground truth dataset consisting of 800 images, generated by rotating and cropping a clean image, and created a noisy image dataset by adding random intensities of simulated noise to the ground truth dataset. In addition to comparing the results of the stripe noise removal visually, we performed a quantitative image quality comparison using simulated datasets and 100 images with very different strengths of simulated noise. All results show that the Low-Rank Recovery method has the best performance and robustness for removing gradient stripe noise without losing useful information. Furthermore, a detailed performance comparison of Polynomial fitting and Low-Rank Recovery at different levels of real noise is presented.

Pt-Black-Modified (Hemi)spherical AFM Sensors: In Situ Imaging of Light-Driven Hydrogen Peroxide Evolution.

In this work, we present (hemi)spherical atomic force microscopy (AFM) sensors for the detection of hydrogen peroxide. Platinum-black (Pt-B) was electrodeposited onto conductive colloidal AFM probes or directly at recessed microelectrodes located at the end of a tipless cantilever, resulting in electrocatalytically active cantilever-based sensors that have a small geometric area but, due to the porosity of the films, exhibit a large electroactive surface area. Focused ion beam-scanning electron microscopy tomography revealed the porous 3D structure of the deposited Pt-B. Given the accurate positioning capability of AFM, these probes are suitable for local in situ sensing of hydrogen peroxide and at the same time can be used for (electrochemical) force spectroscopy measurements. Detection limits for hydrogen peroxide in the nanomolar range (LOD = 68 ± 7 nM) were obtained. Stability test and first in situ proof-of-principle experiments to achieve the electrochemical imaging of hydrogen peroxide generated at a microelectrode and at photocatalytically active structured poly(heptazine imide) films are demonstrated. Force spectroscopic data of the photocatalyst films were recorded in ambient conditions, in solution, and by applying a potential, which demonstrates the versatility of these novel Pt-B-modified spherical AFM probes.

High pressure induced formation of carbon nanorods from tetracosane

Morphology control of carbon structures is essential for improving their performance in many applications. Direct pyrolysis of organic precursors, however, usually yields bulk amorphous carbon. Therefore, traditional methods for controlling the morphology of carbon structures involve multistep processes and complex precursor molecules. While various methods have been developed under ambient pressure, the impact of pressure on the morphology of the resulting carbon structures remains unexplored. Herein, we present the synthesis of carbon nanorods by direct pyrolysis of the low-cost aliphatic hydrocarbon tetracosane under high pressure conditions. The diameters of the carbon nanorods are adjusted by simply varying the synthetic pressures. High pressure allows controlling both the nanorod morphology as well as the degree of order, and local conductivity of the thus prepared nanorods has been confirmed by conductive atomic force microscopy measurements. Our method promises a convenient strategy to synthesize carbon structures with controlled morphology and high ordered chemical structure, which opens opportunities for potential electronic and electrochemical applications.

Controlled Sixfold Symmetric Exfoliation of Oriented MoS2 Monolayers by Coulomb Force

AbstractAtoms, molecules, and nanoparticles can be spatially manipulated by an atomic force microscopy (AFM) tip, through van der Waals (vdW) and/or Coulomb forces. These point‐to‐point manipulations are highly accurate at nanoscale, facilitating the construction and modification of nanostructures. Nevertheless, it is difficult to manipulate 2D layers in vdW crystals by an AFM tip, because the tip‐induced attractive force is usually insufficient to outcompete the interlaminar vdW forces. Herein, manipulation of the surface layers on a MoS2 single crystal by a conductive AFM tip is successfully reported. By applying a bias between the tip and MoS2, the Coulomb attractive force allows the topmost MoS2 layers to be picked up. These exfoliated layers are deformed into micron‐sized bubbles with sixfold symmetry, which are composed of high‐quality monolayers and visually reflecting the hexagonal lattice orientation. The underlying mechanisms of the sixfold symmetric exfoliation and the formation of monolayers are discussed by in situ monitoring of the tunneling volt‐ampere characteristics and simulation of the force distribution. The findings open a new route to obtain high‐quality transition metal dichalcogenide (TMD) monolayers and their derived nanostructures on the surface of TMD single crystals for optoelectronic and photonic device applications.

Electrochemical Metallization Memristive Devices with Al Active Electrode Using Engineered Mixed Hexagonal/Orthorhombic Polycrystalline YMnO3

We report electrochemical metallization (ECM) resistive switching in polycrystalline YMnO3 memristive devices using Al as an active electrode. Al/YMnO3/Pt devices exhibit bipolar resistive switching with a high ROFF/RON ratio of 104, low operational voltages of VSet ≈ 1.7 V and VReset ≈ −0.36 V and good retention properties. The resistive switching is intimately linked to the coexistence of the orthorhombic and hexagonal YMnO3 phases. The characterization of these two nanocrystalline phases is realized not only by X‐ray diffraction – which is shown to be unable to reveal the presence of the orthorhombic phase – but also by a set of correlative microscopy and spectroscopy methods (scanning electron microscopy, optical microscopy, Raman spectroscopy and conductive atomic force microscopy). The origin of resistive switching is ascribed to an Al filament‐based electrochemical metallization mechanism that likely occurs along an oxygen‐deficient grain boundary between the hexagonal and orthorhombic nanocrystalline YMnO3 phases. The unique microstructure provided by the mixed polycrystalline phase films allows to use Al as an active electrode in YMnO3‐based ECM cells, and gives perspective for further miniaturization of the devices.

Towards quantification of doping in gallium arsenide nanostructures by low-energy scanning electron microscopy and conductive atomic force microscopy.

We calculate a universal shift in work function of 59.4 meV per decade of dopant concentration change that applies to all doped semiconductors and from this use Monte Carlo simulations to simulate the resulting change in secondary electron yield for doped GaAs. We then compare experimental images of doped GaAs layers from scanning electron microscopy and conductive atomic force microscopy. Kelvin probe force microscopy allows to directly measure and map local work function changes, but values measured are often smaller, typically only around half, of what theory predicts for perfectly clean surfaces.

Impact of Non‐Stoichiometric Phases and Grain Boundaries on the Nanoscale Forming and Switching of HfOx Thin Films

AbstractHfO2 is one of the most common memristive materials and it is widely accepted that oxygen vacancies are prerequisite to reduce the forming voltage of the respective memristive devices. Here, a series of six oxygen engineered substoichiometric HfO2 − x thin films with varying oxygen deficiency is investigated by conductive atomic force microscopy (c‐AFM) and the switching process of substoichiometric films is observed on the nanoscale. X‐ray diffractometry (XRD) exhibits a phase transition from stoichiometric, monoclinic HfO2 toward oxygen deficient, rhombohedral HfO1.7. The conductance of HfO2 − x is increasing with increasing oxygen deficiency, which is consistent with the increasing prevalence of the highly conductive rhombohedral phase. Simultaneously, c‐AFM reveals significant local conductivity differences between grains and grain boundaries, regardless of the level of oxygen deficiency. Single grains of highly oxygen deficient samples are formed at significant lower voltages. The mean forming voltage is reduced from (7.0 ± 0.6) V for HfO2 to (1.9 ± 0.8) V for HfO1.7. Resistive switching on the nanoscale is established for single grains for the highest deficient thin film samples. The final resistance state is thereby dependent on the initial conductivity of the grains. These studies offer valuable insights into the switching behavior of memristive polycrystalline HfO2.