Conductive Atomic Force Microscopy Research Articles

Strong Covalent Coupling in Vertically Layered SnSe2/PTAA Heterojunctions Enabled High Performance Inorganic-Organic Hybrid Photodetectors.

Controllable large-scale integration of two-dimensional (2D) materials with organic semiconductors and the realization of strong coupling between them still remain challenging. Herein, we demonstrate a wafer-scale, vertically layered SnSe2/PTAA heterojunction array with high light-trapping ability via a low-temperature molecular beam epitaxy method and a facile spin-coating process. Conductive probe atomic force microscopy (CP-AFM) measurements reveal strong rectification and photoresponse behavior in the individual SnSe2 nanosheet/PTAA heterojunction. Theoretical analysis demonstrates that vertically layered SnSe2/PTAA heterojunctions exhibit stronger C-Se covalent coupling than that of the conventional tiled type, which could facilitate more efficient charge transfer. Benefiting from these advantages, the SnSe2/PTAA heterojunction photodetectors with an optimized PTAA concentration show high performance, including a responsivity of 41.02 A/W, an external quantum efficiency of 1.31 × 104%, and high uniformity. The proposed approach for constructing large-scale 2D inorganic-organic heterostructures represents an effective route to fabricate high-performance broadband photodetectors for integrated optoelectronic systems.

Toward coupling across inorganic/organic hybrid interfaces: polyaniline-coated gold nanoparticles with 4-aminothiophenol as gold-anchoring moieties

AbstractThe chemical binding between metal nanoparticles and (semi-)conductive polymer layers is essential to control the (opto-)electronic properties of such hybrid materials. Current approaches that achieve a conjugated binding of organic (semi-)conductive ligands to metal nanoparticles demonstrated promising functional properties, but are based on tedious multi-step organic synthesis to incorporate the required binding moieties at the chain ends of targeted macromolecular species. Herein, we explore the pre-functionalization of gold nanoparticles with p-aminothiophenol and subsequent surfactant-assisted formation of a poly(aniline) (PANI) shell as a means to access gold/PANI core–shell-type nanoparticles with enhanced conductive properties. Controlled surface deposition of these hybrid nanoparticles is achieved via template-assisted self-assembly. For these surface-deposited nanoparticles, charge transport properties are characterized at the nanoscale by conductive atomic force microscopy measurements and show a significant conductivity increase of our core–shell particles as compared to reference particles formed by conventional surfactant-assisted PANI-shell formation. Graphical Abstract

Thiol Coordination Softens Liquid Metal Particles To Improve On-Demand Conductivity.

Achieving tunable rupturing of eutectic gallium indium (EGaIn) particles holds great significance in flexible electronic applications, particularly pressure sensors. We tune the mechanosensitivity of EGaIn particles by preparing them in toluene with thiol surfactants and demonstrate an improvement over typical preparations in ethanol. We observe, across multiple length scales, that thiol surfactants and the nonpolar solvent synergistically reduce the applied stress requirements for electromechanical actuation. At the nanoscale, dodecanethiol and propanethiol in toluene suppress gallium oxide growth, as characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. Quantitative AFM imaging produces force-indentation curves and height images, while conductive AFM measures current while probing individual EGaIn particles. As the applied force increases, thiolated particles demonstrate intensified softening, rupturing, and stress-induced electrical activation at forces 40% lower than those for bare particles in ethanol. To confirm that thiolation facilitates rupturing at the macroscale, a laser is used to ablate samples of EGaIn particles. Scanning electron microscopy and resistance measurements across macroscopic samples confirm that thiolated EGaIn particles coalesce to exhibit electrical activation at 0.1 W. Particles prepared in ethanol, however, require 3 times higher laser power to demonstrate a similar behavior. This unique collection of advanced techniques demonstrates that our particle synthesis conditions can facilitate on-demand functionality to benefit electronic applications.

Electronic Properties of W’ Twin Walls in Ferroelastic BiVO4

AbstractTopological defects in ferroic materials can exhibit intrinsic properties that differ from the bulk. Here， structural and electronic variations of non‐prominent (W’) ferroelastic twin domain walls are investigated in BiVO4, a widely investigated photocatalytic material. Using aberration‐corrected scanning transmission electron microscopy (STEM), a kink configuration of the sharp ferroelastic twin wall with an altered electronic structure is revealed. Nanoscale conductivity measurements by conductive atomic force microscopy (c‐AFM) show higher conductivity at twin walls compared to non‐conductive bulk domains. Electronic structure investigation by electron energy loss spectroscopy (EELS) shows a higher density of oxygen vacancies and possible polaron accumulation at the wall. These findings reveal the electronic properties of BiVO4 domain walls, which are interesting for nanoscale‐engineered catalytic concepts of BiVO4 and materials design for photochemistry‐relevant applications.

Origin of deactivation of aqueous Na–CO2 battery and mitigation for long-duration energy storage

The development of long-duration energy storage technology is crucial to facilitate the efficient utilization of renewable energy sources while mitigating carbon dioxide production. In this study, we investigate the deactivation and reactivation mechanisms of the aqueous Na–CO2 battery during extended cycling. We have designed the cathode to include non-precious intermetallic catalysts. As the cell undergoes repeated cycles, the voltage polarization during discharge progressively rises, eventually leading to the cell's deactivation and formation of decomposition products clogging the electrode surface. Results obtained from comprehensive characterization techniques, including conductive atomic force microscopy (cAFM), Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and inductively coupled plasma-mass spectrometry provide insight into the decomposition products. We also showcase an electrochemical approach for regeneration of these aqueous cells. Our findings, along with the insights we have gained, provide a path toward creating long-duration systems with self-healing properties.

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

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

Structural, morphological, optical, electrical, and magnetic properties of aluminum-doped CoxCa(0.90−x)Ni0.10Fe2O4 flexible substrate for visible to NIR spectra applications

This paper presents a conductive component tailored to a flexible substrate using Al-doped CoxCa(0.90−x)Ni0.10Fe2O4 (x = 0.25, 0.50, and 0.75) for visible to near-infrared (NIR) spectra in magneto-optical applications. The developed nanoparticles show uniformity, nanosized grains, and capillary nanopore fusion characteristics, which are confirmed by x-ray diffraction (XRD), field emission scanning electron microscopy, and energy-dispersive x-ray spectroscopy analyses, respectively. The XRD analysis revealed crystallite sizes of 33.36, 37.08, and 44.25 nm and particle sizes of 45.6, 34.6, and 31.5 nm for the compositions x = 0.25, 0.50, and 0.75, respectively. The Al-doped nanoparticles are converted to a flexible solid substrate utilizing a polyvinyl alcohol matrix, facilitating conformality to build complex shapes and broadening their application scope. The structure shows higher absorption across 450–720 nm, 480–720 nm, and 200–850 nm spectra for x = 0.25, 0.50, and 0.75, respectively. The distinctive magnetic and electrical properties are also evaluated through magnetic force microscopy and conductive atomic force microscopy, culminating in a substrate with exceptional control over light–matter interactions with smooth surfaces with lower surface roughness. The vibrating sample magnetometer analysis of the substrate shows how varying cobalt content affects magnetic properties relevant for visible to near-infrared (NIR) applications, offering insights into coercivity, magnetization, and retentivity changes at different x values. The perceptible novelties of this work are advancements in material sciences aimed at enhancing light manipulation and flexibility for electronic devices.

Characterization of heterogeneity of CVD graphene on copper foil by scanning probe microscopy and Raman spectroscopy

The comparative analysis of the structural, morphological, and local electrical properties of CVD graphene films synthesized at atmospheric and low pressure CVD growth conditions was carried out. The use of electrical techniques of scanning probe microscopy, such as Kelvin probe force microscopy, scanning capacitance microscopy, electrostatic force microscopy, and conductive atomic-force microscopy for investigation of heterogeneous graphene coverage was discussed. A significant change in the surface potential values was observed indicating the formation of p-type multilayered graphene domains on single layer graphene at low pressure and n-type multilayered graphene films at atmospheric pressure CVD. The effect of Ar flow rate increasing during cooling stage in the temperature range of 700–200 °C causing graphite formation was described. The employment of surface potential spectroscopy allows to indicate the presence of nonlinear phenomena in heterogeneous graphene.

Evolution of the Electronic Properties of Tellurium Crystals with Plasma Irradiation Treatment.

Tellurium exhibits exceptional intrinsic electronic properties. However, investigations into the modulation of tellurium's electronic properties through physical modification are notably scarce. Here, we present a comprehensive study focused on the evolution of the electronic properties of tellurium crystal flakes under plasma irradiation treatment by employing conductive atomic force microscopy and Raman spectroscopy. The plasma-treated tellurium experienced a process of defect generation through lattice breaking. Prior to the degradation of electronic transport performance due to plasma irradiation treatment, we made a remarkable observation: in the low-energy region of hydrogen plasma-treated tellurium, a notable enhancement in conductivity was unexpectedly detected. The mechanism underlying this enhancement in electronic transport performance was thoroughly elucidated by comparing it with the electronic structure induced by argon plasma irradiation. This study not only fundamentally uncovers the effects of plasma irradiation on tellurium crystal flakes but also unearths an unprecedented trend of enhanced electronic transport performance at low irradiation energies when utilizing hydrogen plasma. This abnormal trend bears significant implications for guiding the prospective application of tellurium-based 2D materials in the realm of electronic devices.

Suppressed Electrolyte Decomposition Behavior to Improve Cycling Performance of LiCoO2 under 4.6V through the Regulation of Interfacial Adsorption Forces.

Alleviating the decomposition of the electrolyte is of great significance to improving the cycle stability of cathodes, especially for LiCoO2 (LCO), its volumetric energy density can be effectively promoted by increasing the charge cutoff voltage to 4.6V, thereby supporting the large-scale application of clean energy. However, the rapid decomposition of the electrolyte under 4.6V conditions not only loses the transport carrier for lithium ion, but also produces HF and insulators that destroy the interface of LCO and increase impedance. In this work, the decomposition of electrolyte is effectively suppressed by changing the adsorption force between LCO interface and EC. Density functional theory illustrates the LCO coated with lower electronegativity elements has a weaker adsorption force with the electrolyte, the adsorption energy between LCO@Mg and EC (0.49eV) is weaker than that of LCO@Ti (0.73eV). Meanwhile, based on the results of time of flight secondary ion mass spectrometry, conductivity-atomic force microscopy, in situ differential electrochemical mass spectrometry, soft X-ray absorption spectroscopy, and nuclear magnetic resonance, as the adsorption force increases, the electrolyte decomposes more seriously. This work provides a new perspective on the interaction between electrolyte and the interface of cathode and further improves the understanding of electrolyte decomposition.

A universal calibration method for eliminating topography-dependent current in conductive AFM and its application in nanoscale imaging

A universal calibration method for eliminating topography-dependent current in conductive AFM and its application in nanoscale imaging

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.

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. This work reports 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, it is shown 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 photoconductive and bolometric characteristics of V3O5, which eventually affects the oscillation dynamics. Furthermore, V3O5 is identified as a new bolometric material with a temperature coefficient of resistance (TCR) as high as -4.6% K-1 at 423 K. The utility of these devicesis illustrated by demonstrating in-sensor reservoir computing with reduced computational effort and an optical encoding layer for spiking neural network (SNN), respectively, using a simulated array of devices.

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.

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.