Conductive Atomic Force Microscopy-Ultralow-Current Measurement Systems for Nanoscale Imaging of a Surface's Electrical Properties.

One of the most advanced and versatile nanoscale diagnostic tools is atomic force microscopy. By enabling advanced imaging techniques, it allows us to determine various assets of a surface, including morphological, electrical, mechanical, magnetic, and thermal properties. Measuring local current flow is one of the very important methods of evaluation for, for instance, photovoltaic materials or semiconductor structures and other nanodevices. Due to contact areas, the current densities can easily reach above 1 kA/m2; therefore, special detection/measurement setups are required. They meet the required measurement range, sensitivity, noise level, and bandwidth at the measurement scale. Also, they prevent the sample from becoming damaged and prevent unwanted tip-sample issues. In this paper, we present three different nanoscale current measurement solutions, supported with test results, proving their performance.

Investigation on Junction Contacts of Semiconducting Carbon Nanotube Networks Using Conductive Atomic Force Microscopy.

Semiconductor single-walled carbon nanotube (s-SWNT) networks have gained prominence in electronic devices due to their cost-effectiveness, relatively production-naturality, and satisfactory performance. Configuration, density, and resistance of SWNT-SWNT junctions are considered crucial factors influencing the overall conductivity of s-SWNT networks. In this study, we present a method for inferring the lower bounds of the SWNT-SWNT junction resistance in s-SWNT networks based on conductive atomic force microscopy TUNA images. This method further enables the proposal of a classification for SWNT-SWNT junctions based on the current behavior relative to their surroundings. The three types of SWNT-SWNT junctions are denoted as (i) true contact (T), (ii) poor contact (P), and (iii) false contact (F). Of them, the true and poor contacts, respectively, represent good and poor electrical contact for the subject SWNT-SWNT junctions whose electrical conductivity hardly improves under external tip pressure, while that of the false contact can be further improved by external pressure. Statistical analysis demonstrates that while T-type junctions make a significant contribution to network conductivity, their proportion accounts for only approximately 40%. The P-type and F-type junctions, which constitute over 60% of the total, may be a contributing factor that constrains the overall conductivity of the s-SWNT networks. The height ratio of the junction to the sum of two SWNTs was also observed to exhibit variations among the three types. Finally, we propose a three-dimensional model to elucidate the formation mechanism underlying each type of junction. The present study provides insights into the performance of spontaneous contacts between s-SWNTs in the networks, and the systematic image acquisition and junction classification processes may provide support for future advancements in these networks.

The Effect of Relative Humidity in Conductive Atomic Force Microscopy.

Conductive atomic force microscopy (CAFM) analyzes electronic phenomena in materials and devices with nanoscale lateral resolution, and it is widely used by companies, research institutions, and universities. Most data published in the field of CAFM is collected in air at a relative humidity (RH) of 30-60%. However, the effect of RH in CAFM remains unclear because previous studies often made contradictory claims, plus the number of samples and locations tested is scarce. Moreover, previous studies on this topic did not apply current limitations, which can degrade the CAFM tips and generate false data. This article systematically analyzes the effect of RH in CAFM by applying ramped voltage stresses at over 17,000 locations on ten different samples (insulating, semiconducting, and conducting) under seven different RH. An ultra-reliable setup with a 110-pA current limitation during electrical stresses is employed, and excellent CAFM tip integrity after thousands of tests is demonstrated. It is found that higher RH results in increased currents due to the presence of a conductive water meniscus at the tip/sample junction, which increases the effective area for electron flow. This trend is observed in insulators and ultra-thin semiconductors; however, in thicker semiconductors the electron mean free path is high enough to mask this effect. Metallic samples show no dependence on RH. This study clarifies the effect of relative humidity in CAFM, enhances understanding of the technique, and teaches researchers how to improve the reliability of their studies in this field.

Revealing the Properties of Electrically Driven Optical Antennas via Conductive Atomic Force Microscope.

Light emission from ultracompact electrically driven optical antennas (EDOAs) has garnered significant attention due to its terahertz modulation bandwidth. Typically, the EDOAs are fixed and nonadjustable once fabricated, thus hindering the attempts to investigate the influence of structural geometry on light emission properties. Here, we propose and demonstrate that the EDOAs can be constructed by carefully manipulating the gold-coated tips of atomic force microscopy operated in conductive mode into contact with the optical antennas covered by insulating film, where the position of the tunnel junction on the antenna surface can be controlled with high accuracy and flexibility. Taking gold nanorod antennas covered by HfO2 film as an example, we found that the highest light generation efficiency is obtained when the tunnel junction is located at the shoulder edge of the nanorod antenna, where the bonding dipolar surface plasmon mode in the junction is spectrally and spatially coupled with the longitudinal radiation mode of the EDOAs. Besides, position variation of the tunnel junction on the nanorod surface also strongly influences the far-field radiation angular distribution and emission spectrum. Numerical simulations are in good agreement with the experimental results. Our findings offer fundamental insights into the influence of structural parameters on the light emission performance of EDOAs, thus leading to better design of EDOAs with high light generation efficiency and powerful functionality.

CsPbI3 Perovskite Quantum Dot-Based WORM Memory Device with Intrinsic Ternary States.

The migration of mobile ionic halide vacancies is usually considered detrimental to the performance and stability of perovskite optoelectronic devices. Taking advantage of this intrinsic feature, we fabricated a CsPbI3 perovskite quantum dot (PQD)-based write-once-read-many-times (WORM) memory device with a simple sandwich structure that demonstrates intrinsic ternary states with a high ON/OFF ratio of 103:102:1 and a long retention time of 104 s. Through electrochemical impedance spectroscopy, we proved that the resistive switching is achieved by the migration of mobile iodine vacancies (VIs) under an electric field to form conductive filaments (CFs). Using in situ conductive atomic force microscopy, we further revealed that the multilevel property arises from the different activation energies for VIs to migrate at grain boundaries and grain interiors, resulting in two distinct pathways for CFs to grow. Our work highlights the potential of CsPbI3 PQD-based WORM devices, showcasing intrinsic multilevel properties achieved in a simple device structure by rationally controlling the drift of ionic defects.

Unveiling Local Current Behavior and Manipulating Grain Homogenization of Perovskite Films for Efficient Solar Cells.

Achieving high power conversion efficiency in perovskite solar cells (PSCs) heavily relies on fabricating homogeneous perovskite films. However, understanding microscopic-scale properties such as current generation and open-circuit voltage within perovskite crystals has been challenging due to difficulties in quantifying intragrain behavior. In this study, the local current intensity within state-of-the-art perovskite films mapped by conductive atomic force microscopy reveals a distinct heterogeneity, which exhibits a strong anticorrelation to the external biases. Particularly under different external bias polarities, specific regions in the current mapping show contrasting conductivity. Moreover, grains oriented differently exhibit varied surface potentials and currents, leading us to associate this local current heterogeneity with the grain orientation. It was found that the films treated with isopropanol exhibit ordered grain orientation, demonstrating minimized lattice heterogeneity, fewer microstructure defects, and reduced electronic disorder. Importantly, devices exhibiting an ordered orientation showcase elevated macroscopic optoelectronic properties and boosted device performance. These observations underscore the critical importance of fine-tuning the grain homogenization of perovskite films, offering a promising avenue for further enhancing the efficiency of PSCs.

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.

Molecular Junctions for Terahertz Switches and Detectors.

Molecular electronics targets tiny devices exploiting the electronic properties of the molecular orbitals, which can be tailored and controlled by the chemical structure and configuration of the molecules. Many functional devices have been experimentally demonstrated; however, these devices were operated in the low-frequency domain (mainly dc to MHz). This represents a serious limitation for electronic applications, although molecular devices working in the THz regime have been theoretically predicted. Here, we experimentally demonstrate molecular THz switches at room temperature. The devices consist of self-assembled monolayers of molecules bearing two conjugated moieties coupled through a nonconjugated linker. These devices exhibit clear negative differential conductance behaviors (peaks in the current-voltage curves), as confirmed by ab initio simulations, which were reversibly suppressed under illumination with a 30 THz wave. We analyze how the THz switching behavior depends on the THz wave properties (power and frequency), and we benchmark that these molecular devices would outperform actual THz detectors.

Optoelectronic Properties of Cold Plasma-Deposited, Oxidized Sn-C Thin Films.

We report on investigating the structural and electronic properties of semiconducting and insulating layers produced in a process resembling percolation in a unique cold plasma fabrication method (plasma-enhanced chemical vapor deposition-PECVD). Amorphous carbon-tin films (Sn-C) produced from tetramethyl tin (TMT) with an acoustic-frequency glow discharge in a three-electrode reactor were investigated. The layers, after air exposure, oxidized to SnO2/Sn-C. Depending on the coupling capacitance applied to the plasma reactor, the films could be obtained in the form of an amorphous semiconductor or an amorphous insulator. We assume that the semiconductor consists of an internal network of channels auto-organized during deposition. The insulator does not demonstrate any internal structure features. An investigation on conductive filaments creating low-dimensional (LD) nanojunctions in the semiconductor and the location of energetic levels in the insulator was performed. The main parameters of the electronic band structure of the insulating film, such as the transport gap EG (5.2 eV), optical gap Eopt (3.1 eV), electron affinity Χ (2.1 eV), and ionization potential J (7.3 eV), were determined. We have demonstrated a simple approach for developing a catalyst candidate consisting of amorphous semiconductor-insulator nanojunctions for (photo)catalytic hydrogen evolution or CO2 reduction.

Identification the Role of Grain Boundaries in Polycrystalline Photovoltaics via Advanced Atomic Force Microscope.

Atomicforce microscopy (AFM)-based scanning probing techniques, including Kelvinprobe force microscopy (KPFM) and conductive atomic force microscopy (C-AFM), have been widely applied to investigate thelocal electromagnetic, physical, or molecular characteristics of functional materials on a microscopic scale. The microscopic inhomogeneities of the electronic properties of polycrystalline photovoltaic materials can be examined by these advanced AFM techniques, which bridge the local properties of materials to overall device performance and guide the optimization of the photovoltaic devices. In this review, the critical roles of local optoelectronic heterogeneities, especially at grain interiors (GIs) and grain boundaries (GBs) of polycrystalline photovoltaic materials, including versatile polycrystalline silicon, inorganic compound materials, and emerging halide perovskites, studied by KPFM and C-AFM, are systematically identified. How the band alignment and electrical properties of GIs and GBs affect the carrier transport behavior are discussed from the respective of photovoltaic research. Further exploiting the potential of such AFM-based techniques upon a summary of their up-to-date applications in polycrystalline photovoltaic materials is beneficial to acomprehensive understanding of the design and manipulation principles of thenovel solar cells and facilitating the development of the next-generation photovoltaics and optoelectronics.

Local mapping of surface potential in pentacene thin film under gate bias voltage obtained by scanning kelvin probe microscopy.

We report the local surface potential mapping of pentacene film prepared by physical vapor deposition with scanning kelvin probe microscopy where the sample is scanned under different gate voltages. Surface topography and the corresponding potential maps were obtained simultaneously. Spatial distribution of the surface potential at a low gate voltage is clearly correlated with topographic features. A lower electrostatic potential was measured at the grain boundaries (GBs), suggesting that GBs behave as hole traps. This observation is bolstered by conductive atomic force microscopy (C-AFM) data, which reveals a higher conductivity within the grains as opposed to the GBs. An increase in gate voltage minimizes the potential differences at the grain and GBs, suggesting a modification in trap occupancy. We expect that these experimental results, along with existing theories, will provide a better understanding of the microstructural-electrical properties of pentacene film. RESEARCH HIGHLIGHTS: Local surface potential mapping of pentacene film with scanning kelvin probe microscopy. Correlation between the surface potential map and topography at a low gate voltage. Decrease of the potential distribution inhomogeneity by the gate voltage increasement. Higher conductivity at inner grain than grain boundary in conductive atomic force microscopy.

Validating the Use of Conductive Atomic Force Microscopy for Defect Quantification in 2D Materials.

Defects significantly affect the electronic, chemical, mechanical, and optical properties of two-dimensional (2D) materials. Thus, it is critical to develop a method for convenient and reliable defect quantification. Scanning transmission electron microscopy (STEM) and scanning tunneling microscopy (STM) possess the required atomic resolution but have practical disadvantages. Here, we benchmark conductive atomic force microscopy (CAFM) by a direct comparison with STM in the characterization of transition metal dichalcogenides (TMDs). The results conclusively demonstrate that CAFM and STM image identical defects, giving results that are equivalent both qualitatively (defect appearance) and quantitatively (defect density). Further, we confirm that CAFM can achieve single-atom resolution, similar to that of STM, on both bulk and monolayer samples. The validation of CAFM as a facile and accurate tool for defect quantification provides a routine and reliable measurement that can complement other standard characterization techniques.

Spatial variations of conductivity of self-assembled monolayers of dodecanethiol on Au/mica and Au/Si substrates.

Determining the conductivity of molecular layers is a crucial step in advancing towards applications in molecular electronics. A common test bed for fundamental investigations on how to acquire this conductivity are alkanethiol layers on gold substrates. A widely used approach in measuring the conductivity of a molecular layer is conductive atomic force microscopy. Using this method, we investigate the influence of a rougher and a flatter gold substrate on the lateral variation of the conductivity. We find that the roughness of the substrate crucially defines this variation. We conclude that it is paramount to adequately choose a gold substrate for investigations on molecular layer conductivity.

Current-Limited Conductive Atomic Force Microscopy.

Conductive atomic force microscopy (CAFM) has become the preferred tool of many companies and academics to analyze the electronic properties of materials and devices at the nanoscale. This technique scans the surface of a sample using an ultrasharp conductive nanoprobe so that the contact area between them is very small (<100 nm2) and it can measure the properties of the sample with a very high lateral resolution. However, measuring relatively low currents (∼1 nA) in such small areas produces high current densities (∼1000 A/cm2), which almost always results in fast nanoprobe degradation. That is not only expensive but also endangers the reliability of the data collected because detecting which data sets are affected by tip degradation can be complex. Here, we show an inexpensive long-sought solution for this problem by using a current limitation system. We test its performance by measuring the tunneling current across a reference ultrathin dielectric when applying ramped voltage stresses at hundreds of randomly selected locations of its surface, and we conclude that the use of a current limitation system increases the lifetime of the tips by a factor of ∼50. Our work contributes to significantly enhance the reliability of one of the most important characterization techniques in the field of nanoelectronics.

The Role of SnO2 Processing on Ionic Distribution in Double-Cation-Double Halide Perovskites.

Moving toward a future of efficient, accessible, and less carbon-reliant energy devices has been at the forefront of energy research innovations for the past 30 years. Metal-halide perovskite (MHP) thin films have gained significant attention due to their flexibility of device applications and tunable capabilities for improving power conversion efficiency. Serving as a gateway to optimize device performance, consideration must be given to chemical synthesis processing techniques. Therefore, how does common substrate processing techniques influence the behavior of MHP phenomena such as ion migration and strain? Here, we demonstrate how a hybrid approach of chemical bath deposition (CBD) and nanoparticle SnO2 substrate processing significantly improves the performance of (FAPbI3)0.97(MAPbBr3)0.03 by reducing micro-strain in the SnO2 lattice, allowing distribution of K+ from K-Cl treatment of substrates to passivate defects formed at the interface and produce higher current in light and dark environments. X-ray diffraction reveals differences in lattice strain behavior with respect to SnO2 substrate processing methods. Through use of conductive atomic force microscopy (c-AFM), conductivity is measured spatially with MHP morphology, showing higher generation of current in both light and dark conditions for films with hybrid processing. Additionally, time-of-flight secondary ionization mass spectrometry (ToF-SIMS) observed the distribution of K+ at the perovskite/SnO2 interface, indicating K+ passivation of defects to improve the power conversion efficiency (PCE) and device stability. We show how understanding the role of ion distribution at the SnO2 and perovskite interface can help reduce the creating of defects and promote a more efficient MHP device.

Solid Platinum Nanoprobes for Highly Reliable Conductive Atomic Force Microscopy.

Conductive atomic force microscopy (CAFM) is a powerful technique to investigate electrical and mechanical properties of materials and devices at the nanoscale. However, its main challenge is the reliability of the probe tips and their interaction with the samples. The most common probe tips used in CAFM studies are made of Si coated with a thin (∼20 nm) film of Pt or Pt-rich alloys (such as Pt/Ir), but this can degrade fast due to high current densities (>102A/cm2) and mechanical frictions. Si tips coated with doped diamond and solid doped diamond tips are more durable, but they are significantly more expensive and their high stiffness often damages the surface of most samples. One growing alternative is to use solid Pt tips, which have an intermediate price and are expected to be more durable than metal-coated silicon tips. However, a thorough characterization of the performance of solid Pt probes for CAFM research has never been reported. In this article, we characterize the performance of solid Pt probes for nanoelectronics research by performing various types of experiments and compare them to Pt/Ir-coated Si probes. Our results indicate that solid Pt probes exhibit a lateral resolution that is very similar to that of Pt/Ir-coated Si probes but with the big advantage of a much longer lifetime. Moreover, the probe-to-probe deviation of the electrical data collected is small. The use of solid Pt probes can help researchers to enhance the reliability of their CAFM experiments.

Enhanced Thermoelectricity in Metal-[60]Fullerene-Graphene Molecular Junctions.

The thermoelectric properties of molecular junctions consisting of a metal Pt electrode contacting [60]fullerene derivatives covalently bound to a graphene electrode have been studied by using a conducting-probe atomic force microscope (c-AFM). The [60]fullerene derivatives are covalently linked to the graphene via two meta-connected phenyl rings, two para-connected phenyl rings, or a single phenyl ring. We find that the magnitude of the Seebeck coefficient is up to nine times larger than that of Au-C60-Pt molecular junctions. Moreover, the sign of the thermopower can be either positive or negative depending on the details of the binding geometry and on the local value of the Fermi energy. Our results demonstrate the potential of using graphene electrodes for controlling and enhancing the thermoelectric properties of molecular junctions and confirm the outstanding performance of [60]fullerene derivatives.

Direct Imaging of Ion Migration in Amorphous Oxide Electronic Synapses with Intrinsic Analog Switching Characteristics.

Amorphous metal oxides with analog resistive switching functions (i.e., continuous controllability of the electrical resistance) are gaining emerging interest due to their neuromorphic functionalities promising for energy efficient electronics. The mechanisms are currently attributed to field-driven migration of the constituent ions, but the applications are being hindered by the limited understanding of the physical mechanisms due to the difficulty in analyzing the causal ion migration, which occurs on a nanometer or even atomic scale. Here, the direct electrical transport measurement of analog resistive switching and ångström scale imaging of the causal ion migration is demonstrated in amorphous TaOx (a-TaOx) by conductive atomic force microscopy. Atomically flat thin films of a-TaOx, which is a practical material for commercial resistive random access memory, are fabricated in this study, and the mechanisms of the three known types of analog resistive switching phenomena (current-dependent set, voltage-dependent reset, and time-dependent switching) are directly visualized on the surfaces. The observations indicate that highly analog type of resistive switching can be induced in a-TaOx by inducing the continuous redox reactions for 2.0 < x < 2.5, which are characteristic of a-TaOx. The measurements also demonstrate drastic control of the switching stochasticity, which is attributable to controlled segregation of a metastable a-TaO2 phase. The findings provide direct clues for tuning the analog resistive switching characteristics of amorphous metal oxides and developing new functions for future neuromorphic computing.

3D Nanoprinting of All-Metal Nanoprobes for Electric AFM Modes.

3D nanoprinting via focused electron beam induced deposition (FEBID) is applied for fabrication of all-metal nanoprobes for atomic force microscopy (AFM)-based electrical operation modes. The 3D tip concept is based on a hollow-cone (HC) design, with all-metal material properties and apex radii in the sub-10 nm regime to allow for high-resolution imaging during morphological imaging, conductive AFM (CAFM) and electrostatic force microscopy (EFM). The study starts with design aspects to motivate the proposed HC architecture, followed by detailed fabrication characterization to identify and optimize FEBID process parameters. To arrive at desired material properties, e-beam assisted purification in low-pressure water atmospheres was applied at room temperature, which enabled the removal of carbon impurities from as-deposited structures. The microstructure of final HCs was analyzed via scanning transmission electron microscopy-high-angle annular dark field (STEM-HAADF), whereas electrical and mechanical properties were investigated in situ using micromanipulators. Finally, AFM/EFM/CAFM measurements were performed in comparison to non-functional, high-resolution tips and commercially available electric probes. In essence, we demonstrate that the proposed all-metal HCs provide the resolution capabilities of the former, with the electric conductivity of the latter onboard, combining both assets in one design.

Imaging Phase Segregation in Nanoscale LixCoO2 Single Particles.

LixCoO2 (LCO) is a common battery cathode material that has recently emerged as a promising material for other applications including electrocatalysis and as electrochemical random access memory (ECRAM). During charge-discharge cycling LCO exhibits phase transformations that are significantly complicated by electron correlation. While the bulk phase diagram for an ensemble of battery particles has been studied extensively, it remains unclear how these phases scale to nanometer dimensions and the effects of strain and diffusional anisotropy at the single-particle scale. Understanding these effects is critical to modeling battery performance and for predicting the scalability and performance of electrocatalysts and ECRAM. Here we investigate isolated, epitaxial LiCoO2 islands grown by pulsed laser deposition. After electrochemical cycling of the islands, conductive atomic force microscopy (c-AFM) is used to image the spatial distribution of conductive and insulating phases. Above 20 nm island thicknesses, we observe a kinetically arrested state in which the phase boundary is perpendicular to the Li-planes; we propose a model and present image analysis results that show smaller LCO islands have a higher conductive fraction than larger area islands, and the overall conductive fraction is consistent with the lithiation state. Thinner islands (14 nm), with a larger surface to volume ratio, are found to exhibit a striping pattern, which suggests surface energy can dominate below a critical dimension. When increasing force is applied through the AFM tip to strain the LCO islands, significant shifts in current flow are observed, and underlying mechanisms for this behavior are discussed. The c-AFM images are compared with photoemission electron microscopy images, which are used to acquire statistics across hundreds of particles. The results indicate that strain and morphology become more critical to electrochemical performance as particles approach nanometer dimensions.