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.

SiC Doping Impact during Conducting AFM under Ambient Atmosphere.

The characterization of silicon carbide (SiC) by specific electrical atomic force microscopy (AFM) modes is highly appreciated for revealing its structure and properties at a nanoscale. However, during the conductive AFM (C-AFM) measurements, the strong electric field that builds up around and below the AFM conductive tip in ambient atmosphere may lead to a direct anodic oxidation of the SiC surface due to the formation of a water nanomeniscus. In this paper, the underlying effects of the anodization are experimentally investigated for SiC multilayers with different doping levels by studying gradual SiC epitaxial-doped layers with nitrogen (N) from 5 × 1017 to 1019 at/cm3. The presence of the water nanomeniscus is probed by the AFM and analyzed with the force-distance curve when a negative bias is applied to the AFM tip. From the water meniscus breakup distance measured without and with polarization, the water meniscus volume is increased by a factor of three under polarization. AFM experimental results are supported by electrostatic modeling to study oxide growth. By taking into account the presence of the water nanomeniscus, the surface oxide layer and the SiC doping level, a 2D-axisymmetric finite element model is developed to calculate the electric field distribution nearby the tip contact and the current distributions at the nanocontact. The results demonstrate that the anodization occurred for the conductive regime in which the current depends strongly to the doping; its threshold value is 7 × 1018 at/cm3 for anodization. Finally, the characterization of a classical planar SiC-MOSFET by C-AFM is examined. Results reveal the local oxidation mechanism of the SiC material at the surface of the MOSFET structure. AFM topographies after successive C-AFM measurements show that the local oxide created by anodization is located on both sides of the MOS channel; these areas are the locations of the highly n-type-doped zones. A selective wet chemical etching confirms that the oxide induced by local anodic oxidation is a SiOCH layer.

Three-Dimensional Reconstruction of Conductive Filaments in HfOx -Based Memristor.

HfOx -based memristor has been studied extensively as one of the most promising memories for the excellent nonvolatile data storage and computing-in-memory capabilities. However, the resistive switching mechanism, relying on the formation and rupture of conductive filaments (CFs) during device operations, is still under debate. In this work, the CFs with different morphologies after different operations-forming, set, and reset-are clearly revealed for the first time by 3D reconstruction of conductive atomic force microscopy (c-AFM) images. Intriguingly, multiple CFs are successfully observed in HfOx -based memristor devices with three different resistive states. CFs after forming, set, and reset exhibit the typical morphologies of hourglass, inverted-cone, and short-cone, respectively. The rupture location of CFs after the reset operation is also observed clearly. These findings reveal the microscopic behaviors underlying the resistive switching, which could pave the road to design and optimize oxide-based memristors for both memory and computing applications.

Nanoscale Control of the Metal-Insulator Transition at LaAlO3/KTaO3 Interfaces.

Recent reports of superconductivity at KTaO3 (KTO) (110) and (111) interfaces have sparked intense interest due to the relatively high critical temperature as well as other properties that distinguish this system from the more extensively studied SrTiO3 (STO)-based heterostructures. Here, we report the reconfigurable creation of conducting structures at intrinsically insulating LaAlO3/KTO(110) and (111) interfaces. Devices are created using two distinct methods previously developed for STO-based heterostructures: (1) conductive atomic-force microscopy lithography and (2) ultralow-voltage electron-beam lithography. At low temperatures, KTO(110)-based devices show superconductivity that is tunable by an applied back gate. A one-dimensional nanowire device shows single-electron-transistor (SET) behavior. A KTO(111)-based device is metallic but does not become superconducting. These reconfigurable methods of creating nanoscale devices in KTO-based heterostructures offer new avenues for investigating mechanisms of superconductivity as well as development of quantum devices that incorporate strong spin-orbit interactions, superconducting behavior, and nanoscale dimensions.

Atomic-Scale Imaging and Nano-Scale Mapping of Cubic α-CsPbI3 Perovskite Nanocrystals for Inverted Perovskite Solar Cells.

Colloidal synthesized cubic α-CsPbI3 perovskite nanocrystals having a smaller lattice constant (a = 6.2315 Å) compared to the standard structure, and nanoscale mapping of their surfaces are reported to achieve superior photovoltaic performance under 45-55% humidity conditions. Atomic scale transmission electron microscopic images have been utilized to probe the precise arrangement of Cs, Pb, and I atoms in a unit cell of α-CsPbI3 NCs, which is well supported by the VESTA structure. Theoretical calculation using density functional theory of our experimental structure reveals the realization of direct band to band transition with a lower band gap, a higher absorption coefficient, and stronger covalent bonding between the Pb and I atoms in the [PbI6]4- octahedral, as compared to reported standard structure. Nanoscale surface mapping using Kelvin probe force microscopy yielding contact potential difference (CPD) and conductive atomic force microscopy for current mapping have been employed on α-CsPbI3 NCs films deposited on different DMSO doped PEDOT:PSS layers. The difference of CPD value under dark and light illumination suggests that the hole injection strongly depends on the interfaces with PEDOT:PSS layer. The carrier transport through grain interiors and grain boundaries in α-CsPbI3 probed by the single-point c-AFM measurements reveal the excellent photosensitivity under the light conditions. Finally, inverted perovskite solar cells, employing α-CsPbI3 NCs film as an absorber layer and PEDOT:PSS layer as a hole transport layer, have been optimized to achieve the highest power conversion efficiency of 10.6%, showing their potential for future earth abundant, low cost, and air stable inverted perovskite photovoltaic devices.

Translational PET Imaging of Spinal Cord Injury with the Serotonin Transporter Tracer [11C]AFM.

PURPOSE: The descending raphespinal serotonin (5-HT) system contributes to neural activities required for locomotion. The presynaptic serotonin transporter (SERT) is a marker of 5-HT innervation. In this study, we explored the use of PET imaging with the SERT radioligand [11C]AFM as a biomarker of 5-HT axon damage after spinal cord injury (SCI) in a rodent model and its translation to imaging SCI in humans. PROCEDURES: PET imaging with [11C]AFM was performed in healthy rats under baseline and citalopram blocking conditions and a mid-thoracic transection rat model of SCI. The lumbar-to-cervical activity (L/C) ratio was calculated for the healthy and SCI animals to assess SERT binding decrease after SCI. Finally, translation of [11C]AFM PET was attempted to explore its potential to image SCI in humans. RESULTS: Intense uptake in the brain and intact spinal cord was observed at 30-60 min post-injection of [11C]AFM in healthy rats. About 65% of [11C]AFM uptake in the spinal cord was blocked by citalopram. In the SCI rat model, the cervical uptake of [11C]AFM was similar to that in healthy rats, but the lumbar uptake was dramatically reduced, resulting in about half the L/C ratio in SCI rats compared to healthy rats. In contrast, [11C]AFM uptake in the human spinal cord showed no obvious decrease after treatment with citalopram. In the human subjects with SCI, decreases in [11C]AFM uptake were also not obvious in the section of spinal cord caudal to the injury point. CONCLUSION: [11C]AFM PET imaging of SERT provides a useful preclinical method to non-invasively visualize the rodent spinal cord and detect SERT changes in SCI rodent models. However, there appears to be little detectable specific binding signal for [11C]AFM in the human spinal cord. An SERT tracer with higher affinity and lower non-specific binding signal is needed to image the spinal cord in humans and to assess the axonal status in SCI patients.

Multiscale Investigation of the Structural, Electrical and Photoluminescence Properties of MoS2 Obtained by MoO3 Sulfurization.

In this paper, we report a multiscale investigation of the compositional, morphological, structural, electrical, and optical emission properties of 2H-MoS2 obtained by sulfurization at 800 °C of very thin MoO3 films (with thickness ranging from ~2.8 nm to ~4.2 nm) on a SiO2/Si substrate. XPS analyses confirmed that the sulfurization was very effective in the reduction of the oxide to MoS2, with only a small percentage of residual MoO3 present in the final film. High-resolution TEM/STEM analyses revealed the formation of few (i.e., 2-3 layers) of MoS2 nearly aligned with the SiO2 surface in the case of the thinnest (~2.8 nm) MoO3 film, whereas multilayers of MoS2 partially standing up with respect to the substrate were observed for the ~4.2 nm one. Such different configurations indicate the prevalence of different mechanisms (i.e., vapour-solid surface reaction or S diffusion within the film) as a function of the thickness. The uniform thickness distribution of the few-layer and multilayer MoS2 was confirmed by Raman mapping. Furthermore, the correlative plot of the characteristic A1g-E2g Raman modes revealed a compressive strain (ε ≈ -0.78 ± 0.18%) and the coexistence of n- and p-type doped areas in the few-layer MoS2 on SiO2, where the p-type doping is probably due to the presence of residual MoO3. Nanoscale resolution current mapping by C-AFM showed local inhomogeneities in the conductivity of the few-layer MoS2, which are well correlated to the lateral changes in the strain detected by Raman. Finally, characteristic spectroscopic signatures of the defects/disorder in MoS2 films produced by sulfurization were identified by a comparative analysis of Raman and photoluminescence (PL) spectra with CVD grown MoS2 flakes.

Visualization of a hexagonal born nitride monolayer on an ultra-thin gold film via reflected light microscopy.

Hexagonal boron nitride (h-BN) is an important insulating layered material for two-dimensional heterostructure devices. Among many applications, few-layer h-BN films have been employed as superior tunneling barrier films. However, it is difficult to construct a heterostructure with ultra-thin h-BN owing to the poor visibility of flakes on substrates, especially on a metallic surface substrate. Since reflectance from a metallic surface is generally high, a h-BN film on a metallic surface does not largely influence reflection spectra. In the present study, a thin Au layer with a thickness of ∼10 nm deposited on a Si substrate with a thermally grown SiO2was used for visualizing h-BN flakes. The thin Au layer possesses conductivity and transparency. Thus, the Au/SiO2/Si structure serves as an electrode and contributes to the visualization of an ultra-thin film according to optical interference. As a demonstration, the wavelength-dependent contrast of exfoliated few-layer h-BN flakes on the substrate was investigated under a quasi-monochromatic light using an optical microscope. A monolayer h-BN film was recognized in the image taken by a standard digital camera using a narrow band-pass filter of 490 nm, providing maximum contrast. Since the contrast increases linearly with the number of layers, the appropriate number of layers is identified from the contrast. Furthermore, the insulating property of a h-BN flake is examined using a conductive atomic force microscope to confirm whether the thin Au layer serves as an electrode. The tunneling current through the h-BN flake is consistent with the number of layers estimated from the contrast.

Elucidating the Spatial Dynamics of Charge Carriers in Quasi-Two-Dimensional Perovskites.

Quasi-two dimensional (2D) organic-inorganic hybrid perovskites (OIHPs) have shown better ambient stability with decent solar cell performances. However, the power conversion efficiency of quasi-2D OIHPs is still below that of 3D polycrystalline perovskites. To understand the limitation of quasi-2D OIHPs, we explore charge carrier properties in 3D and quasi-2D perovskites using advanced scanning probe microscopy techniques. Kelvin probe force microscopy (KPFM) identifies slow degradation in quasi-2D perovskites by measuring photovoltage variations under thermal and humid conditions. Bias-driven photocurrent maps obtained by conductive-atomic force microscopy (c-AFM) measurements reveal local inhomogeneous conduction and hysteretic currents in quasi-2D perovskites while relatively uniform conductivity is observed on individual grains in the 3D perovskite counterparts. In addition, bias-driven KPFM and I-V measurements in the lateral Au electrode devices show higher charge carrier dynamics with stronger potential drop at the interfaces in the 3D perovskite than those of the quasi-2D perovskite devices. The combination of c-AFM and KPFM results confirm less ionic conduction in the quasi-2D perovskites as compared to the 3D perovskites. Our study elucidates underlying mechanisms behind the lower efficiency of quasi-2D perovskites, which is necessary for further development of efficient and stable perovskite-based devices.

Electrical conductivity measurement ofλDNA molecules by conductive atomic force microscopy.

Conductive atomic force microscopy (C-AFM) is a powerful tool used in the microelectronics analysis by applying a certain bias voltage between the conducting probe and the sample and obtaining the electrical information of sample. In this work, the surface morphological information and current images of the lambda DNA (λDNA) molecules with different distributions were obtained by C-AFM. The 1 and 10 ngµl-1DNA solutions were dripped onto mica sheets for making randomly distributed DNA and DNA network samples, and another 1 ngµl-1DNA sample was placed in a DC electric field with a voltage of 2 V before being dried for stretching the DNA sample. The results show that the current flowing through DNA networks was significantly higher than the stretched and random distribution of DNA in the experiment. TheI-Vcurve of DNA networks was obtained by changing the bias voltage of C-AFM from -9 to 9 V. The currents flowing through stretched DNA at different pH values were studied. When the pH was 7, the current was the smallest, and the current was gradually increased as the solution became acidic or alkaline.

Advanced atomic force microscopy-based techniques for nanoscale characterization of switching devices for emerging neuromorphic applications.

Neuromorphic systems require integrated structures with high-density memory and selector devices to avoid interference and recognition errors between neighboring memory cells. To improve the performance of a selector device, it is important to understand the characteristics of the switching process. As changes by switching cycle occur at local nanoscale areas, a high-resolution analysis method is needed to investigate this phenomenon. Atomic force microscopy (AFM) is used to analyze the local changes because it offers nanoscale detection with high-resolution capabilities. This review introduces various types of AFM such as conductive AFM (C-AFM), electrostatic force microscopy (EFM), and Kelvin probe force microscopy (KPFM) to study switching behaviors.

Nanoscale Study of the Hole-Selective Passivating Contacts with High Thermal Budget Using C-AFM Tomography.

We investigate hole-selective passivating contacts that consist of an interfacial layer of silicon oxide (SiOx) and a layer of boron-doped SiCx(p). The fabrication process of these contacts involves an annealing step at temperatures above 750 °C which crystallizes the initially amorphous layer and diffuses dopants across the interfacial oxide into the wafer to facilitate charge transport, but it can also disrupt the SiOx layer necessary for wafer-surface passivation. To investigate the transport mechanism of the charge carriers through the selective contact and its changes during the annealing process, we utilize various characterization methods, such as transmission electron microscopy, micro Raman spectroscopy, and conductive atomic force microscopy. Combining the latter with a sequential removal of material, we assemble a tomographic reconstruction of the crystallized layer that reveals the presence of preferential vertical transport channels.

Templating effect of single-layer graphene supported by an insulating substrate on the molecular orientation of lead phthalocyanine.

The influence of single-layer graphene on top of a SiO2/Si surface on the orientation of nonplanar lead phthalocyanine (PbPc) molecules is studied using two-dimensional grazing incidence X-ray diffraction. The studies indicate the formation of a mixture of polymorphs, i.e., monoclinic and triclinic forms of PbPc with face-on (lying down) and edge-on (standing up) PbPc orientations, respectively. The formation of monoclinic fractions is attributed to the presence of the graphene layer directing the π interactions between the highly delocalized macrocycles. The competing interfacial van der Waals forces and molecule-molecule interactions lead to the formation of a small fraction of triclinic moieties. The nanoscale electrical characterization of the thin PbPc layer on graphene by means of conducting atomic force microscopy shows enhanced vertical conductance with interconnected conducting domains consisting of ordered monoclinic crystallites through which the charge transfer occurs via tunneling. These results show the importance of a templating layer to induce the formation of a required phase of PbPc suitable for specific device applications.

Understanding Interlayer Contact Conductance in Twisted Bilayer Graphene.

Bilayer or few-layer 2D materials showing novel electrical properties in electronic device applications have aroused increasing interest in recent years. Obtaining a comprehensive understanding of interlayer contact conductance still remains a challenge, but is significant for improving the performance of bilayer or few-layer 2D electronic devices. Here, conductive atomic force microscope (C-AFM) experiments are reported to explore the interlayer contact conductance between bilayer graphene (BLG) with various twisted stacking structures fabricated by the chemical vapor deposition (CVD) method. The current maps show that the interlayer contact conductance between BLG strongly depends on the twist angle. The interlayer contact conductance of 0° AB-stacking bilayer graphene (AB-BLG) is ≈4 times as large as that of 30° twisted bilayer graphene (t-BLG), which indicates that the twist angle-dependent interlayer contact conductance originates from the coupling-decoupling transitions. Moreover, the moiré superlattice-level current images of t-BLG show modulations of local interlayer contact conductance. Density functional theory calculations together with a theoretical model reproduce the C-AFM current map and show that the modulation is mainly attributed to the overall contribution of local interfacial carrier density and tunneling barrier.

Temperature-Dependent Local Electrical Properties of Organic-Inorganic Halide Perovskites: In Situ KPFM and c-AFM Investigation.

Organic-inorganic halide perovskite materials are emerging as a new class of photoelectric materials for its low cost, easy preparation, and, especially, outstanding optoelectronic properties. Although tremendous efforts have been made on the regulation and optimization of perovskite materials and their microscopic electrical properties for high-efficiency solar cells, few reports focus on the evolution of electrical properties with temperature changes, especially at the microscopic scale, which will directly affect the device performances at varying temperatures. Here, we map the contact potential difference and photocurrent distribution of MAPbI3 at different temperatures in situ by Kelvin probe force microscopy and conductive atomic force microscopy, emphasizing the different influences of variable temperature and phase transition on the photoelectric properties of grains and grain boundaries (GBs). It is discovered that both the Fermi level and photocurrent decrease as the sample is heated from 30 to 80 °C gradually because of the variation of effective carrier concentration and the degradation of carrier mobility implicated by lattice vibration scattering. The difference between the Fermi level at GBs and that on the grains ascends first and then descends, peaking at 50 °C, near which MAPbI3 transforms from a tetragonal phase to a cubic phase. This peak is speculated as a comprehensive consequence of the increasing difference of the Fermi level of semiconductors with different doping concentrations and the converging properties of grains and GBs with the temperature rising because the lower ion activation energy of the cubic phase at higher temperatures facilitates greatly the ions' movement between grains and GB. The variation trend of the difference of the photocurrent is the same. These findings advance the knowledge on the temperature-induced variations of microscopic photoelectrical properties of organic-inorganic hybrid perovskite materials, which may guide the development of strategies for improving their thermal stability.

Realization of Diverse Waveform Converters from a Single Nanoscale Lateral p-n Junction Cu2S-CdS Heterostructure.

A differentiator is an electronic component used to accomplish mathematical operations of calculus functions of differentiation for shaping different waveforms. Differentiators are used in numerous areas of electronics, including electronic analog computers, wave-shaping circuits, and frequency modulators. Conventional differentiators are fabricated using active operational amplifiers or using passive resistor-capacitor combinations. Here, we report that a single Cu2S-CdS heterostructure acts as a differentiator for performing numerical functions of input waveform conversion into different shapes. When a rectangular wave signal is applied through the tip of a conductive atomic force microscope, a spikelike wave signal is obtained from the Cu2S-CdS heterostructure. The Cu2S-CdS differentiator is able to convert a sine wave signal into a cosine wave signal and a triangular wave signal into a square wave signal similar to the classical differentiators. The finding of a nanoscale differentiator at extremely small length scales may have profound applications in different domains of electronics.

Extreme Reconfigurable Nanoelectronics at the CaZrO3 /SrTiO3 Interface.

Complex oxide heterostructures have fascinating emergent properties that originate from the properties of the bulk constituents as well as from dimensional confinement. The conductive behavior of the polar/nonpolar LaAlO3 /SrTiO3 interface can be reversibly switched using conductive atomic force microscopy (c-AFM) lithography, enabling a wide range of devices and physics to be explored. Here, extreme nanoscale control over the CaZrO3 /SrTiO3 (CZO/STO) interface, which is formed from two materials that are both nonpolar, is reported. Nanowires with measured widths as narrow as 1.2 nm are realized at the CZO/STO interface at room temperature by c-AFM lithography. These ultrathin nanostructures have spatial dimensions at room temperature that are comparable to single-walled carbon nanotubes, and hold great promise for alternative oxide-based nanoelectronics, as well as offer new opportunities to investigate the electronic structure of the complex oxide interfaces. The cryogenic properties of devices constructed from quasi-1D channels, tunnel barriers, and planar gates exhibit gate-tunable superconductivity, quantum oscillations, electron pairing outside of the superconducting regime, and quasi-ballistic transport. This newly demonstrated ability to control the metal-insulator transition at nonpolar oxide interface greatly expands the class of materials whose behavior can be patterned and reconfigured at extreme nanoscale dimensions.

Nanoscale electrochemical response of lithium-ion cathodes: a combined study using C-AFM and SIMS.

The continuous demand for improved performance in energy storage is driving the evolution of Li-ion battery technology toward emerging battery architectures such as 3D all-solid-state microbatteries (ASB). Being based on solid-state ionic processes in thin films, these new energy storage devices require adequate materials analysis techniques to study ionic and electronic phenomena. This is key to facilitate their commercial introduction. For example, in the case of cathode materials, structural, electrical and chemical information must be probed at the nanoscale and in the same area, to identify the ionic processes occurring inside each individual layer and understand the impact on the entire battery cell. In this work, we pursue this objective by using two well established nanoscale analysis techniques namely conductive atomic force microscopy (C-AFM) and secondary ion mass spectrometry (SIMS). We present a platform to study Li-ion composites with nanometer resolution that allows one to sense a multitude of key characteristics including structural, electrical and chemical information. First, we demonstrate the capability of a biased AFM tip to perform field-induced ionic migration in thin (cathode) films and its diagnosis through the observation of the local resistance change. The latter is ascribed to the internal rearrangement of Li-ions under the effect of a strong and localized electric field. Second, the combination of C-AFM and SIMS is used to correlate electrical conductivity and local chemistry in different cathodes for application in ASB. Finally, a promising starting point towards quantitative electrochemical information starting from C-AFM is indicated.

Graphene-Complex-Oxide Nanoscale Device Concepts.

The integration of graphene with complex-oxide heterostructures such as LaAlO3/SrTiO3 offers the opportunity to combine the multifunctional properties of an oxide interface with the exceptional electronic properties of graphene. The ability to control interface conduction through graphene and understanding how it affects the intrinsic properties of an oxide interface are critical to the technological development of multifunctional devices. Here we demonstrate several device archetypes in which electron transport at an oxide interface is modulated using a patterned graphene top-gate. Nanoscale devices are fabricated at the oxide interface by conductive atomic force microscope (c-AFM) lithography, and transport measurements are performed as a function of the graphene gate voltage. Experiments are performed with devices written adjacent to or directly underneath the graphene gate. Distinct capabilities of this approach include the ability to create highly flexible device configurations, the ability to modulate carrier density at the oxide interface, and the ability to control electron transport up to the single-electron tunneling regime, while maintaining intrinsic transport properties of the oxide interface. Our results facilitate the design of a variety of nanoscale devices that combine excellent transport properties of these two proximal two-dimensional electron systems.

Direct Mapping of Phase Separation across the Metal-Insulator Transition of NdNiO3.

Perovskite rare-earth nickelates RNiO3 are prototype correlated oxides displaying a metal-insulator transition (MIT) at a temperature tunable by the ionic radius of the rare-earth R. Although its precise origin remains a debated topic, the MIT can be exploited in various types of applications, notably for resistive switching and neuromorphic computation. So far, the MIT has been mostly studied by macroscopic techniques, and insights into its nanoscale mechanisms were only provided recently by X-ray photoemission electron microscopy through absorption line shifts, used as an indirect proxy to the resistive state. Here, we directly image the local resistance of NdNiO3 thin films across their first-order MIT using conductive-atomic force microscopy. Our resistance maps reveal the nucleation of ∼100-300 nm metallic domains in the insulating state that grow and percolate as temperature increases. We discuss the resistance contrast mechanism, analyze the microscopy and transport data within a percolation model, and propose experiments to harness this mesoscopic electronic texture in devices.