Kelvin Probe Force Microscopy Research Articles

Regulating Oxygen Vacancies and Fermi Level of Mesoporous CeO2-x for Intensified Built-In Electric Field and Boosted Charge Separation of Cs3 Bi2 Br9 /CeO2-x S-Scheme Heterojunction.

Regulating the built-in electric field (BEF) in the heterojunction is is a great challenge in developing high-efficiency photocatalysts. Herein, by tailoring the content of oxygen vacancies in the constituent reduction semiconductor (mesoporous CeO2-x ), a precise Fermi level (EF ) regulation of CeO2-x is realized, yielding an amplified EF gap and intensified BEF in the Cs3 Bi2 Br9 perovskite quantum dots/CeO2-x S-scheme heterojunction. Such an enhanced BEF offers a strong driving force for directional electron transfer, boosting charge separation in the S-scheme heterojunction. As a result, the optimized Cs3 Bi2 Br9 /CeO2-x heterojunction delivers a remarkable CO2 conversion efficiency, with an impressive CO production rate of 80.26µmolg-1 h-1 and a high selectivity of 97.6%. The S-scheme charge transfer mode is corroborated comprehensively by density functional theory (DFT) calculations, insitu X-ray photoelectron spectroscopy (XPS), and photo-irradiated Kelvin probe force microscopy (KPFM). Moreover, diffuse reflectance infrared Fourier transform spectra (DRIFTS) and theoretical calculations are conducted cooperatively to reveal the CO2 photoreduction pathway.

A Flexible and Stretchable Temperature Sensor Based on Contact Electrification for Robotic Sensing

With the rapid development of robotic systems, an increasing number of various sensitive sensors are needed to meet the requirement of data collection for unmanned detection and monitoring technology. Among various external stimuli information, temperature sensing is an essential important function that can avoid high-temperature scalding injuries, achieve robot detection of environmental, and human-machine interfaces applications. However, most of the existing temperature sensors for robotic sensing are realized by rigid materials, which have the disadvantage of not being able to adapt to an arbitrarily curved surface. Also, most of the sensors are thermistor-based approaches, which faces challenges in developing a low-cost robotic system since external power is required to obtain the sensing signal. In this work, a self-powered and stretchable temperature sensor based on Triboelectric Nanogenerator (TENG) technology was developed. The principle of TENG is the coupling effect of triboelectric charge transfer and electrostatic induction effects, which can generate different magnitudes of electrical signals when subjected to external stimuli, including temperature. To this end, this study is a pilot effort toward validating the sensitivity of TENG electrical output on different temperature effects. The surface potential of materials is explored under different temperatures by Kelvin probe force microscopy (KPFM), which shows the feasibility of self-powered temperature sensor. The proposed temperature sensor is composed of highly resilient materials physiological saline as liquid electrode encapsulated with Ecoflex as triboelectric layer, which has the advantage of biocompatibility. The temperature sensing performance was successfully maintained at 200% stretch. Owing to its flexible, bendable and stretchable characteristics, the self-powered temperature-sensitive sensor has been successfully demonstrated on a robot hand, which can read the information and respond to different temperatures through the feedback system. Overall, this self-powered temperature-sensitive sensor has great potential to be an emerging tool for human-robot interaction and automatic detection.

Unraveling Spatial Charge Density Distributions at Electrode-Electrolyte Interfaces

Charge distributions at electrode-electrolyte interfaces play a crucial role in many electrochemical processes, some of which are electrocatalysis, supercapacitors, batteries etc., However, most experimental techniques, either microscopy or spectroscopy tools that are used to probe these systems, cannot provide any information about the interfacial spatial charge distribution. Techniques based on kelvin-probe force microscopy (KPFM) can provide some information, however they have a very limited depth of resolution and can only work with extremely dilute electrolytes. Recently, we developed a technique known as charge profiling three-dimensional (3D) atomic force microscopy (CP-3D-AFM) which could map out the charge densities at angstrom-depth resolution. The method is based on measuring 3D-AFM maps at different electrode potentials and further using electrostatic calculations to obtain the charge density depth profiles at the respective potentials. We used this method to measure charge distributions in highly ionic electrolyte systems and can explain their differential capacitance profiles. This CP-3D-AFM technique could enable to obtain molecular structural insights for a wide range of electrolyte systems and serve in designing principles for engineering effective electrode-electrolyte interfaces.

Influence of Atmospheric Contaminants on the Work Function of Graphite.

Airborne hydrocarbon contamination occurs rapidly on graphitic surfaces and negatively impact many of their material properties, yet much of the molecular details of the contamination remains unknown. We use Kelvin probe force microscopy (KPFM) to study the time evolution of the surface potential of graphite exposed to ambient. After exfoliation in air, the surface potential of graphite is not homogeneous and contains features that are absent in the topography image. In addition, the heterogeneity of the surface potential images increased in the first few days followed by a decrease at longer exposure times. These observations are strong support of slow conformation change, phase separation, and/or dynamic displacement of the adsorbed airborne contaminants.

Unraveling the photocatalytic performance of rGO/Nd2O3/MoO3 ternary nanocomposite with organic dyes using scanning Kelvin probe

In this study, we investigated the efficiency of visible-light activated rGO/Nd2O3/MoO3 ternary nanocomposite for the degradation of methylene blue (MB), rose bengal (RB), and real-time industrial effluent (RTIE) samples for wastewater treatment. The samples were characterized via XRD, Raman, UV–vis, FT-IR, FESEM/EDX, Zeta-potential, and Scanning Kelvin Probe (SKP) techniques. Crystalline nature and structure were identified using XRD and Raman. The bandgap of prepared samples was calculated from absorption spectra obtained from the UV–vis absorption spectroscopy. FT-IR analysis determined the function groups in rGO, MoO3, rGO/Nd2O3, and rGO/Nd2O3/MoO3. Furthermore, the morphology and elemental composition percentage of pure nanoparticles and nanocomposite were confirmed by FESEM/EDX. The surface area and pore size were evaluated using BET-BJH. Work function evaluated from a novel approach SKP in the dark (5.25 eV) and under light (5.02 eV) exposure indicating the formation of the new energy level of charge carriers, minimizing electron-hole recombination rate. The maximum photodegradation efficiency of the hybrid rGO/Nd2O3/MoO3 nanocomposite was ∼ 99% for MB and ∼ 95% for RB under visible light. Our investigations unravel the mechanism behind the photodegradation process of model dyes and industrial effluents with rGO/Nd2O3/MoO3, which will create a new pathway in wastewater treatment applications.

Quantification of Hydrogen Flux from Atmospheric Corrosion of Steel Using the Scanning Kelvin Probe Technique

The atmospheric corrosion of high-strength steels can lead to hydrogen absorption directly linked to hydrogen embrittlement or delayed fracture phenomena. A scanning Kelvin probe (SKP) and electrochemical permeation technique (EPT) were applied to correlate the potential of an oxidized surface with the flux of hydrogen across a thin steel membrane. The side of the membrane opposite the corroding or electrochemically charged area was analyzed. The potential drop in the oxide was calibrated in terms of surface hydrogen activity, and SKP can be applied in situ for the mapping of hydrogen distribution in the corroding metal. A very low flux of hydrogen can be characterized and quantified by SKP, which is typically observed under atmospheric corrosion conditions. Therefore, hydrogen localization that drives steel durability under atmospheric corrosion conditions can be evaluated.

Multifractality in Surface Potential for Cancer Diagnosis.

Recent advances in high-resolution biomedical imaging have improved cancer diagnosis, focusing on morphological, electrical, and biochemical properties of cells and tissues, scaling from cell clusters down to the molecular level. Multiscale imaging revealed high complexity that requires advanced data processing methods of multifractal analysis. We performed label-free multiscale imaging of surface potential variations in human ovarian cancer cells using Kelvin probe force microscopy (KPFM). An improvement in the differentiation between nonmalignant and cancerous cells by multifractal analysis using adaptive versus median threshold for image binarization was demonstrated. The results reveal the multifractality of cancer cells as a new biomarker for cancer diagnosis.

Novel through-holes g-C3N4/BiOBr S-scheme heterojunction: Charge relocation mechanism and DFT insights

A novel multiscale through-holes g-C3N4/BiOBr S-scheme heterojunction with homogeneous morphology was fabricated via a solvothermal method. Notably, the prepared through-holes g-C3N4 yielded a subband gap (2.11 eV) attributed to the fracture and reorganization of triazine ring units, leading to a narrow band gap complex. Photocatalyst A-2 (2.73 eV) was significantly broadened at the absorption edge. A reasonable S-scheme heterojunction charge relocation mechanism was demonstrated based on active species trapping experiments, atomic force microscope (AFM) equipped with a Kelvin probe force microscope (KPFM), and density functional theoretical (DFT) theoretical calculations. The S-scheme g-C3N4/BiOBr heterojunction and the constructed internal electric field facilitate the retention of high redox properties and facilitated charge relocation. Hence, the synergistic interaction between the S-scheme heterojunction and through-holes structure enabled specimens to be exhibited high-efficiency degradation activity. The degradation efficiency of photocatalyst A-2 for TC·HCL and RhB was 94.5% (60 min) and 99.9% (30 min), respectively. At pH = 5.1, the TC·HCL photoreaction time was reduced to 30 min, whereas at pH = 2.3, the RhB photoreaction time was shortened to 15 min. Five repeatable recovery tests still maintain excellent stability. This work contributes new insights into the charge relocation mechanism of S-scheme heterojunction high-efficiency photocatalysts.

Application of the [WO2(C5H7O2)2] Complex in Hydrothermal Synthesis of WO3 Film and Study of Its Electrochromic Properties

The goal of this work was the synthesis study of the [WO2(C5H7O2)2] complex and its application as a precursor for the growth of WO3 films in hydrothermal conditions, as well as evaluating the microstructural features and electrochromic properties of the formed materials. Dioxotungsten acetylacetonate was synthesized in an aqueous medium and purified. It was found that during hydrothermal treatment of the alcohol solution of the complex, acetylacetonate ligands undergo partial destructive substitution by alkoxyl groups, intensifying at temperatures above 140 °C. Considering these data and using a [WO2(C5H7O2)2] solution, WO3 films were grown on glass and glass/ITO substrates. The resulting films had different microstructures according to scanning electron microscopy (SEM) and atomic force microscopy (AFM): the former consisted of submicron spheres (~500 nm), distinct nanoparticles (60–160 nm), and submicron- and micron-sized ridges, while the latter consisted of 1D structures (length 350 ± 25 nm, width 110 ± 25 nm). Using Kelvin probe force microscopy (KPFM), the electron work function was determined for the film on glass/ITO substrate (4.77 eV). It was found that the electrochemical coloration process of the obtained WO3 film can proceed in two stages, and the optical contrast is about 17.5% (at the wavelengths of 600–1100 nm). The results obtained show the prospects of applying the proposed approach to obtaining WO3 electrochromic films with a hierarchical microstructure with the hydrothermal method using the [WO2(C5H7O2)2] complex as a precursor.

Hydrothermal Synthesis of a Cellular NiO Film on Carbon Paper as a Promising Way to Obtain a Hierarchically Organized Electrode for a Flexible Supercapacitor.

The formation of a cellular hierarchically organized NiO film on a carbon paper substrate under hydrothermal conditions using triethanolamine as a base has been studied. The thermal behavior of the carbon paper substrate with the applied semi-product shell was studied using synchronous thermal analysis (TGA/DSC) and it was demonstrated that such modification of the material surface leads to a noticeable increase in its thermal stability. Using scanning electron microscopy (SEM), it was shown that the NiO film grown on the carbon fiber surface is characterized by a complex cellular morphology, organized by partially layered individual nanosheets of about 4-5 nm thickness and lateral dimensions up to 1-2 μm, some edges and folds of which are located vertically relative to the carbon fiber surface. The surface of the obtained material was also examined using atomic force microscopy (AFM), and the electronic work function of the oxide shell surface was evaluated using the Kelvin probe force microscopy (KPFM) method. The electrochemical parameters of the obtained flexible NiO/CP electrode were analyzed: the dependence of the specific capacitance on the current density was determined and the stability of the material during cycling was studied, which showed that the proposed approach is promising for manufacturing hierarchically organized electrodes for flexible supercapacitors.

Triboelectric nanogenerators with ultrahigh current density enhanced by hydrogen bonding between nylon and graphene oxide

The triboelectric properties of the tribolayers are essential factors affecting the current density of triboelectric nanogenerators (TENGs). To enhance the current density, composites have been developed to tune their triboelectric properties. Previous studies have reported enhanced TENG performance with composite materials, primarily based on their composition, while chemical interactions between the components have been less analyzed. In this study, we report a novel approach to improve the current density of a TENG by introducing dipole-dipole interactions between a nylon filter membrane and graphene oxide (GO) through hydrogen bonds. The Raman spectroscopy confirmed the occurrence of the interactions resulting from hydrogen bonding. The enhancing mechanisms of hydrogen bonds were further analyzed by Kelvin probe force microscope (KPFM) measurement, which demonstrated that hydrogen bonding could influence the surface potential of the coated GO, leading to increased output of the nylon/GO@NFM TENG (NGN-TENG). Our results show that an ultrahigh current density of 1757 mA·m−2 was obtained with a 2 × 2 cm2 NGN-TENG. Additionally, we demonstrated the feasibility of using the NGN-TENG as a motion sensor to sense finger motions. These findings suggest that the introduction of hydrogen bonds in TENG composites can provide a promising route for improving their performance.

Biological Activity and Thrombogenic Properties of Oxide Nanotubes on the Ti-13Nb-13Zr Biomedical Alloy.

The success of implant treatment is dependent on the osseointegration of the implant. The main goal of this work was to improve the biofunctionality of the Ti-13Nb-13Zr implant alloy by the production of oxide nanotubes (ONTs) layers for better anchoring in the bone and use as an intelligent carrier in drug delivery systems. Anodization of the Ti-13Nb-13Zr alloy was carried out in 0.5% HF, 1 M (NH4)2SO4 + 2% NH4F, and 1 M ethylene glycol + 4 wt.% NH4F electrolytes. Physicochemical characteristics of ONTs were performed by high-resolution electron microscopy (HREM), X-ray photoelectron spectroscopy (XPS), and scanning Kelvin probe (SKP). Water contact angle studies were conducted using the sitting airdrop method. In vitro biological properties and release kinetics of ibuprofen were investigated. The results of TEM and XPS studies confirmed the formation of the single-walled ONTs of three generations on the bi-phase (α + β) Ti-13Nb-13Zr alloy. The ONTs were composed of oxides of the alloying elements. The proposed surface modification method ensured good hemolytic properties, no cytotoxity for L-929 mouse cells, good adhesion, increased surface wettability, and improved athrombogenic properties of the Ti-13Nb-13Zr alloy. Nanotubular surfaces allowed ibuprofen to be released from the polymer matrix according to the Gallagher-Corrigan model.

Analysis of multi-center topological domain states in BiFeO3 nanodot arrays

High-density ferroelectric BiFeO3 (BFO) nanodot arrays were developed through template-assisted tailoring of epitaxial thin films. By combining piezoresponse force microscopy (PFM) and Kelvin probe force microscopy (KPFM) imaging techniques, we found that oxygen vacancies in nanodot arrays can be transported in the presence of an electric field. Besides triple-center domains, quadruple-center domains with different vertical polarizations were also identified. This was confirmed by combining the measurements of the domain switching and polarization vector distribution. The competition between the accumulation of mobile charges, such as oxygen vacancies, on the interface and the geometric constraints of nanodots led to the formation of these topological domain states. These abnormal multi-center topological defect states pave the way for improving the storage density of ferroelectric memory devices.

Selective Growth of van der Waals Heterostructures Enabled by Electron-Beam Irradiation.

Van der Waals heterostructures (vdWHSs) enable the fabrication of complex electronic devices based on two-dimensional (2D) materials. Ideally, these vdWHSs should be fabricated in a scalable and repeatable way and only in the specific areas of the substrate to lower the number of technological operations inducing defects and impurities. Here, we present a method of selective fabrication of vdWHSs via chemical vapor deposition by electron-beam (EB) irradiation. We distinguish two growth modes: positive (2D materials nucleate on the irradiated regions) on graphene and tungsten disulfide (WS2) substrates, and negative (2D materials do not nucleate on the irradiated regions) on the graphene substrate. The growth mode is controlled by limiting the air exposure of the irradiated substrate and the time between irradiation and growth. We conducted Raman mapping, Kelvin-probe force microscopy, X-ray photoelectron spectroscopy, and density-functional theory modeling studies to investigate the selective growth mechanism. We conclude that the selective growth is explained by the competition of three effects: EB-induced defects, adsorption of carbon species, and electrostatic interaction. The method here is a critical step toward the industry-scale fabrication of 2D-materials-based devices.

Unveiling localized electronic properties of ReS2 thin layers at nanoscale using Kelvin force probe microscopy combined with tip-enhanced Raman spectroscopy

Electronic properties of two-dimensional (2D) materials can be strongly modulated by localized strain. The typical spatial resolution of conventional Kelvin probe force microscopy (KPFM) is usually limited in a few hundreds of nanometers, and it is difficult to characterize localized electronic properties of 2D materials at nanoscales. Herein, tip-enhanced Raman spectroscopy (TERS) is proposed to combine with KPFM to break this restriction. TERS scan is conducted on ReS2 bubbles deposited on a rough Au thin film to obtain strain distribution by using the Raman peak shift. The localized contact potential difference (CPD) is inversely calculated with a higher spatial resolution by using strain measured by TERS and CPD-strain working curve obtained using conventional KPFM and atomic force microscopy. This method enhances the spatial resolution of CPD measurements and can be potentially used to characterize localized electronic properties of 2D materials.

The Effect of Reduction and Oxidation Processes on the Work Function of Metal Oxide Crystals: TiO2(110) and SrTiO3(001) Case

The strict control of the work function of transition metal oxide crystals is of the utmost importance not only to fundamental research but also to applications based on these materials. Transition metal oxides are highly abundant in electronic devices, as their properties can be easily modified using redox processes. However, this ease of tuning is a double-edged sword. With the ease of manipulation comes difficulty in controlling the corresponding process. In this study, we demonstrate how redox processes can be induced in a laboratory setting and how they affect the work function of two model transition metal oxide crystals, namely titanium dioxide TiO2(110) and strontium titanate SrTiO3(001). To accomplish this task, we utilized Kelvin Probe Force Microscopy (KPFM) to monitor changes in work function, Scanning Tunneling Microscopy (STM), and Low-Energy Electron Diffraction (LEED) to check the surface morphology and reconstruction, and we also used X-ray Photoelectron Spectroscopy (XPS) to determine how the surface composition evolves. We also show that using redox processes, the work function of titanium dioxide can be modified in the range of 3.4–5.0 eV, and that of strontium titanate can be modified in the range of 2.9–4.5 eV. Moreover, we show that the presence of an oxygen-gaining material in the vicinity of a transition metal oxide during annealing can deepen the changes to its stoichiometry and therefore the work function.

Nanoscale electrical characterization of ambient-induced surface impurities on high-nickel cathode materials for lithium-ion batteries

One of the most critical points in the study of LIB-related materials is the extremely high reactivity of Li. In addition to pure Li metal, many Li-containing materials employed in LIBs are highly reactive under ambient conditions. Therefore, they should be stored and treated in an inert environment, such as vacuum chambers and gloveboxes filled with inert gases. In particular, most pristine cathode materials contain Li and are more reactive in air than pristine anode materials are. For instance, various impurities, mostly Li2CO3, are grown on the surface of pristine NCA (LiNixCoyAlzO2, x + y + z = 1) materials. The precise characterization of these ambient-induced surface impurities is critical for understanding the intrinsic properties of these cathode materials. In this study, we directly image and characterize ambient-induced surface impurities formed on the surface of high-Ni NCA (LiNi0.8Co0.15Al0.05O2) materials using Kelvin probe force microscopy (KPFM) and scanning spreading resistance microscopy (SSRM). The ambient-induced surface impurities show clearly distinguishable work functions and resistance features compared with the pristine NCA surface. In particular, it is confirmed that the resistance of ambient-induced impurities is significantly higher than that of pristine NCA materials, which can deteriorate the performance of LIB cells. This study provides direction for the fabrication, storage, and processing of LIB cathode materials.

Mercury Ion Sensing Using Aptamer-Modified Extended Gate Field-Effect Transistors and a Handheld Device

In this research, we have designed, fabricated, and characterized an Electrical double-layer (EDL) gated FET platform to detect heavy metals. The electrical double layer (EDL)-gated field-effect transistor-based sensor is garnering interest due to its sensitivity, portable configuration, selectivity, inexpensive operation, as well as their user-friendly nature. the sensing platform designed for rapid detection of Hg2+ using DNA-based aptamers. The investigation was carried out by introducing different concentrations of Mercury ions and a lower detection limit of 1 μM was achieved. The sensor surface was validated with Kelvin Probe Force Microscope (KPFM), which is consistent with the electrical response obtained. Sensor selectivity was studied and exhibited a high sensitivity toward Mercury ion detection. Considering its limit of detection, compatibility, and fast turnaround; the proposed system has the potential to be used to detect Mercury ions instantly for environmental monitoring, where quick and accurate detection of Mercury ions is essential.

Dislocation-assisted localised pitting corrosion behaviour of Al[sbnd]Si[sbnd]Mg[sbnd]Cu[sbnd]Mn alloy

The effects of the electrochemical nature of intermetallic particles (IMPs) and dislocation density on the localised pitting corrosion behaviour of AlSiMgCuMn alloy was investigated. The Cu-rich Q-phase and Mn-rich α-AlFeMnSi particles cause the anodic dissolution of adjacent Al, leading to localised pitting. Kelvin-probe atomic force microscopy studies revealed that the high potential of Q-phase and α-AlFeMnSi particles renders them cathodic. Therefore, micro-galvanic coupling arises between these IMPs and the surrounding Al. High dislocation densities in Al regions adjacent to the IMPs exacerbated localised pitting, which causes stress localisation and deteriorates the overall corrosion resistance of the alloy.

Ohmic-functionalized type I heterojunction: Improved alkaline water splitting and photocatalytic conversion from CO2 to C2H2

A hollow dodecahedron-shaped N-doped carbon (N-C) coated with CoSe2 nanoparticles are fabricated via MOF-derived self-sacrificing strategy based on Kirkendall Effect. By coupling with CdS nanodots, the optimal Ohmic-type functionalized type I heterojunction CdS/N-C/CoSe2 (CCE50) exhibits a significant photocatalytic hydrogen evolution reaction (PHER) rate of 19317.3 μmol h−1 gcat−1 that is 15.7 and 33.7 folds higher than type I CdS/N-C heterojunction (1230.3 μmol h−1 gcat−1) and pure CdS respectively, and successfully transfers the source of photo-corrosion to obtain stable PHER for 5 cycles. Moreover, the CCE50 in alkaline media (pH = 12) achieves a 1.6-fold PHER rate higher than that in the original triethanolamine (TEOA) aqueous solution (pH≈8), where electron paramagnetic resonance (EPR) result shows that it is attributed to the accumulation of O2–. The effective PHER rate can be attributed to the synergistic effect of higher light absorption in hollow CCE50 with multiple scattering and the introduction of Ohmic contact. Besides, the successful conversion from CO2 to C2H2 under 80 kPa CO2 pressure is detected firstly on CdS-based photocatalyst (the conversion rate is 2.8 μmol h−1 gcat−1) without other C1 or C2 gas products. EPR, in-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) tests, Kelvin Probe Force Microscopy (KPFM) and density functional theory calculations, etc. have illustrated and verified the photocatalytic mechanism for Ohmic contact-enhancing type I heterojunction, which promotes hydrogen production in alkaline media and C2H2 generation from CO2.