Imaging Graphene Moiré Superlattices via Scanning Kelvin Probe Microscopy.

Moiré superlattices in van der Waals heterostructures are gaining increasing attention because they offer new opportunities to tailor and explore unique electronic phenomena. Using a combination of lateral piezoresponse force microscopy (LPFM) and scanning Kelvin probe microscopy (SKPM), we directly correlate ABAB and ABCA stacked graphene with local surface potential. We find that the surface potential of the ABCA domains is ∼15 mV higher (smaller work function) than that of the ABAB domains. First-principles calculations show that the different work functions between ABCA and ABAB domains arise from the stacking-dependent electronic structure. Moreover, while the moiré superlattice visualized by LPFM can change with time, imaging the surface potential distribution via SKPM appears more stable, enabling the mapping of ABAB and ABCA domains without tip-sample contact-induced effects. Our results provide a new means to visualize and probe local domain stacking in moiré superlattices along with its impact on electronic properties.

In Operando Visualization of Interfacial Band Bending in Photomultiplying Organic Photodetectors.

Charge injection is a basic transport process that strongly affects performance of optoelectronic devices such as light-emitting diodes and photodetectors. In these devices, the charge injection barrier is related to the band bending at the active layer/electrode interface and exhibits sophisticated dependence on interface structure and device operating conditions, making it difficult to determine via either theoretical prediction or experimental measurements. Here, in operando cross-sectional scanning Kelvin probe microscopy (SKPM) has been applied in organic photodetectors to visualize the interfacial band bending. The photoinduced interfacial band bending becomes more significant with increasing reverse bias voltage, resulting in reduced charge injection barrier and facilitated charge injection. The photoinduced injection current is orders of magnitude higher than the photocurrent directly generated from light absorption and thus leads to significant photomultiplication. Furthermore, the interfacial structure is tuned to further enhance photoinduced interfacial band bending and the photomultiplication factor.

Photolon Nanoporous Photoactive Material with Antibacterial Activity and Label-Free Noncontact Method for Free Radical Detection.

The worldwide increase in bacterial resistance and healthcare-associated bacterial infections pose a serious threat to human health. The antimicrobial photodynamic method reveals the opportunity for a new therapeutic approach that is based on the limited delivery of photosensitizer from the material surface. Nanoporous inorganic-organic composites were obtained by entrapment of photosensitizer Photolon in polysiloxanes that was prepared by the sol-gel method. The material was characterized by its porosity, optical properties (fluorescence and absorbance), and laser-induced antimicrobial activity against Staphylococcus epidermidis, Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli. The permanent encapsulation of Photolon in the silica coating and the antimicrobial efficiency was confirmed by confocal microscope and digital holotomography. The generation of free radicals from nanoporous surfaces was proved by scanning Kelvin probe microscopy. For the first time, it was confirmed that Kelvin probe microscopy can be a label-free, noncontact alternative to other conventional methods based on fluorescence or chemiluminescence probes, etc. It was confirmed that the proposed photoactive coating enables the antibacterial photodynamic effect based on free radicals released from the surface of the coating. The highest bactericidal efficiency of the proposed coating was 87.16%. This coating can selectively limit the multiplication of bacterial cells, while protecting the environment and reducing the risk of surface contamination.

Revealing Strain-Induced Effects in Ultrathin Heterostructures at the Nanoscale.

Two-dimensional materials are being increasingly studied, particularly for flexible and wearable technologies because of their inherent thickness and flexibility. Crucially, one aspect where our understanding is still limited is on the effect of mechanical strain, not on individual sheets of materials, but when stacked together as heterostructures in devices. In this paper, we demonstrate the use of Kelvin probe microscopy in capturing the influence of uniaxial tensile strain on the band-structures of graphene and WS2 (mono- and multilayered) based heterostructures at high resolution. We report a major advance in strain characterization tools through enabling a single-shot capture of strain defined changes in a heterogeneous system at the nanoscale, overcoming the limitations (materials, resolution, and substrate effects) of existing techniques such as optical spectroscopy. Using this technique, we observe that the work-functions of graphene and WS2 increase as a function of strain, which we attribute to the Fermi level lowering from increased p-doping. We also extract the nature of the interfacial heterojunctions and find that they get strongly modulated from strain. We observe that the strain-enhanced charge transfer with the substrate plays a dominant role, causing the heterostructures to behave differently from two-dimensional materials in their isolated forms.

Direct Imaging of Space-Charge Accumulation and Work Function Characteristics of Functional Organic Interfaces.

The tailoring of organic systems is crucial to further extend the efficiency of charge transfer mechanisms and represents a cornerstone for molecular device technologies. However, this demands control of electrical properties and understanding of the physics behind organic interfaces. Here, a quantitative spatial overview of work function characteristics for phthalocyanine architectures on Au substrates is provided via kelvin probe microscopy. While macroscopic investigations are very informative, the current approach offers a nanoscale spatial rendering of electrical characteristics which is not possible to attain via conventional techniques. Interface dipole is observed due to the formation of charge accumulation layers in thin F16 CuPc, F16 CoPc, and MnPc films, displaying work functions of 5.7, 6.1, and 5.0 eV, respectively. The imaging and quantification of interface locations with significant surface potential and work function response (<0.33 eV for material thickness <1 nm) show also a dependency on the crystalline state of the organic systems. The work function mapping suggests space-charge carrier regions of about 4 nm at the organic interface. This reveals rich spatial electric parameters and ambipolar characteristics that may drive electrical performance at device scales, opening a realm of possibilities toward the development of functional organic architectures and its applications.

Density and energy distribution of interface states in the grain boundaries of polysilicon nanowire.

Wafer-scale fabrication of semiconductor nanowire devices is readily facilitated by lithography-based top-down fabrication of polysilicon nanowire (P-SiNW) arrays. However, free carrier trapping at the grain boundaries of polycrystalline materials drastically changes their properties. We present here transport measurements of P-SiNW array devices coupled with Kelvin probe force microscopy at different applied biases. By fitting the measured P-SiNW surface potential using electrostatic simulations, we extract the longitudinal dopant distribution along the nanowires as well as the density of grain boundaries interface states and their energy distribution within the band gap.

Improved Exciton Dissociation at Semiconducting Polymer:ZnO Donor:Acceptor Interfaces via Nitrogen Doping of ZnO.

Exciton dissociation at the zinc oxide/poly(3-hexylthiophene) (ZnO/P3HT) interface as a function of nitrogen doping of the zinc oxide, which decreases the electron concentration from approximately 1019 cm-3 to 1017 cm-3, is reported. Exciton dissociation and device photocurrent are strongly improved with nitrogen doping. This improved dissociation of excitons in the conjugated polymer is found to result from enhanced light-induced de-trapping of electrons from the surface of the nitrogen-doped ZnO. The ability to improve the surface properties of ZnO by introducing a simple nitrogen dopant has general applicability.

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.

Vapor Deposition of Bilayer 3R MoS2 with Room-Temperature Ferroelectricity.

Two-dimensional ultrathin ferroelectrics have attracted much interest due to their potential application in high-density integration of non-volatile memory devices. Recently, 2D van der Waals ferroelectric based on interlayer translation has been reported in twisted bilayer h-BN and transition metal dichalcogenides (TMDs). However, sliding ferroelectricity is not well studied in non-twisted homo-bilayer TMD grown directly by chemical vapor deposition (CVD). In this paper, for the first time, experimental observation of a room-temperature out-of-plane ferroelectric switch in semiconducting bilayer 3R MoS2 synthesized by reverse-flow CVD is reported. Piezoelectric force microscopy (PFM) hysteretic loops and first principle calculations demonstrate that the ferroelectric nature and polarization switching processes are based on interlayer sliding. The vertical Au/3R MoS2/Pt device exhibits a switchable diode effect. Polarization modulated Schottky barrier height and polarization coupling of interfacial deep states trapping/detrapping may serve in coordination to determine switchable diode effect. The room-temperature ferroelectricity of CVD-grown MoS2 will proceed with the potential wafer-scale integration of 2D TMDs in the logic circuit.

Charge trapping by self-assembled monolayers as the origin of the threshold voltage shift in organic field-effect transistors.

The threshold voltage is an important property of organic field-effect transistors. By applying a self-assembled monolayer (SAM) on the gate dielectric, the value can be tuned. After electrical characterization, the semiconductor is delaminated. The surface potentials of the revealed SAM perfectly agree with the threshold voltages, which demonstrate that the shift is not due to the dipolar contribution, but due to charge trapping by the SAM.

Kelvin Probe Microscopy Investigation of Poly-Octylthiophene Aggregates.

Conductive polymers have fundamental relevance as well as novel technological applications in the organic optoelectronics field. Their photophysical and transport properties strongly depend on the molecular arrangement, and nanoscale characterization is needed to fully understand the optoelectronic processes taking place in organic devices. In this work, we study the electrostatic properties of poly-3-octylthiophene isolated structures: disordered low-packed polymer chains and crystalline layered lamellar assemblies. We characterize the electronic ground state using Kelvin probe microscopy. This allows us to resolve a rich variety of surface potential regions that emerge over the different polymer structures. These SP regions are correlated with different molecular aggregates.

Quantitative amplitude-modulation scanning Kelvin probe microscopy via the second eigenmode excitation.

Amplitude modulation scanning Kelvin probe microscopy (AM-SKPM) is widely used to measure the contact potential difference (CPD) between probe and samples in ambient or dry inert atmosphere. However, AM-SKPM is generally considered quantitatively inaccurate due to crosstalk between the cantilever and the sample. Here we demonstrate that the accuracy of AM-SKPM-based CPD measurements is drastically improved by exciting the SKPM probe at its second eigenmode. In the second eigenmode of oscillation, there exists a stationary node at the cantilever towards its free end, across which the displacement bears opposite signs; therefore driving the SKPM probe at its second eigenmode helps to partially cancel the virtual work done by the cantilever and reduce the crosstalk effect. The improvement in accuracy is experimentally confirmed with interdigitating electrodes calibration samples as well as practical samples such as the cross-section of wafer-bonded GaAs/GaN heterojunction.

Balanced Ambipolar Charge Transport in Phenacene/Perylene Heterojunction-Based Organic Field-Effect Transistors.

Electronic devices relying on the combination of different conjugated organic materials are considerably appealing for their potential use in many applications such as photovoltaics, light emission, and digital/analog circuitry. In this study, the electrical response of field-effect transistors achieved through the evaporation of picene and PDIF-CN2 molecules, two well-known organic semiconductors with remarkable charge transport properties, was investigated. With the main goal to get a balanced ambipolar response, various device configurations bearing double-layer, triple-layer, and codeposited active channels were analyzed. The most suitable choices for the layer deposition processes, the related characteristic parameters, and the electrode position were identified to this purpose. In this way, ambipolar organic field-effect transistors exhibiting balanced mobility values exceeding 0.1 cm2 V-1 s-1 for both electrons and holes were obtained. These experimental results highlight also how the combination between picene and PDIF-CN2 layers allows tuning the threshold voltages of the p-type response. Scanning Kelvin probe microscopy (SKPM) images acquired on picene/PDIF-CN2 heterojunctions suggest the presence of an interface dipole between the two organic layers. This feature is related to the partial accumulation of space charge at the interface being enhanced when the electrons are depleted in the underlayer.

Strain-Work Function Relationship in Single-Crystal Tetracene.

Understanding the impact of strain on organic semiconductors is important for the development of electronic devices and sensors that are subject to environmental changes and mechanical stimuli; it is also important for understanding the fundamental mechanisms of charge trapping. Following our previous study on the strain effects in rubrene, we present here only the second example of the strain-work function relationship in an organic semiconductor; in this case, the benchmark material tetracene. Thin, platelike single crystals of tetracene with large (001) facets were laminated onto silicon and rubber substrates having significantly different coefficients of thermal expansion; mechanical strain in tetracene was subsequently induced by varying the temperature of the assembly. Tensile and compressive strains parallel to the (001) major facet were measured by grazing incidence X-ray diffraction, and the corresponding shifts in the electronic work functions were recorded via scanning Kelvin probe microscopy (SKPM). The work function of the tetracene (001) crystal surface directly correlated with the net mechanical strain and increased by ∼100 meV for in-plane tensile strains of 0.1% and decreased by approximately the same amount for in-plane compressive strains of -0.1%. This work provides evidence of the general and important impact of strain on the electrical properties of van der Waals bonded crystalline organic semiconductors and thereby supports the hypothesis that heterogeneous strains, for example in thin films, can be a major source of static electronic disorder.

Scalable Integration of Coplanar Heterojunction Monolithic Devices on Two-Dimensional In2Se3.

The formation of lateral heterojunction arrays within two-dimensional (2D) crystals is an essential step to realize high-density, ultrathin electro-optical integrated circuits, although the assembling of such structures remains elusive. Here we demonstrated a rapid, scalable, and site-specific integration of lateral 2D heterojunction arrays using few-layer indium selenide (In2Se3). We use a scanning laser probe to locally convert In2Se3 into In2O3, which shows a significant increase in carrier mobility and transforms the metal-semiconductor junctions from Schottky to ohmic type. In addition, a lateral p-n heterojunction diode within a single nanosheet is demonstrated and utilized for photosensing applications. The presented method enables high-yield, site-specific formation of lateral 2D In2Se3-In2O3-based hybrid heterojunctions for realizing nanoscale devices with multiple advanced functionalities.

Grain Boundaries as Electrical Conduction Channels in Polycrystalline Monolayer WS2.

We show that grain boundaries (GBs) in polycrystalline monolayer WS2 can act as conduction channels with a lower gate onset potential for field-effect transistors made parallel, compared to devices made in pristine areas and perpendicular to GBs. Localized doping at the GB causes photoluminescence quenching and a reduced Schottky barrier with the metal electrodes, resulting in higher conductivity at lower applied bias values. Samples are grown by chemical vapor deposition with large domains of ∼100 µm, enabling numerous devices to be made within single domains, across GBs and at many similar sites across the substrate to reveal similar behaviors. We corroborate our electrical measurements with Kelvin probe microscopy, highlighting the nature of the doping-type in the material to change at the grain boundaries. Molecular dynamics simulations of the GB are used to predict the atomic structure of the dislocations and meandering tilt GB behavior on the nanoscale. These results show that GBs can be used to provide conduction pathways that are different to transport across GBs and in pristine area for potential electronic applications.

Zn Wetted CeO2 Based Composite Galvanization: An Effective Route To Combat Biofouling.

The present paper reports for the first time the development and application of novel Zn wetted CeO2 (Zn/CeO2) composite galvanic zinc coating to combat microbial induced corrosion (MIC). Zinc metal-metal interaction causes the effective incorporation of composite into the galvanic coating and accordingly increases the active sites for antibiofouling activity. The developed coatings are explored for their anticorrosion/antibiofouling characteristics toward MIC induced by cultured seawater consortia. Enhanced antibiofouling activity of the composite galvanic coating is achieved due to the tuned content of 28 wt % Zn and 34 wt % of Ce. High charge transfer resistance as high as 4.0 × 1014 Ω cm2 and low double layer capacitance as low as 3.99 × 10-8 F are achieved by tuning the structure and composition of the coating. The synergistic effect of Zn and Ce ensures the stability and corrosion resistance of the coatings in a corrosive bacterial environment. Evident decreases in the bacterial attachment and biofilm formation are illustrated using antibiofouling assay. The antibiofouling activity is attributed to the effective reduction of Ce4+ to Ce3+ and the shuttling characteristics of oxidation state of CeO2. This impairs the cellular respiration and results in bacterial death. Thus, it can be used as an effective coating to protect the steel based equipment in corrosive marine environments to combat marine microorganisms and their interactions. The present study also paves the scope for exploration of similar effective protective systems.

Low-Temperature Processed TiOx/Zn1-xCdxS Nanocomposite for Efficient MAPbIxCl1-x Perovskite and PCDTBT:PC70BM Polymer Solar Cells.

The majority of high-performance perovskite and polymer solar cells consist of a TiO2 electron transport layer (ETL) processed at a high temperature (>450 °C). Here, we demonstrate that low-temperature (80 °C) ETL thin film of TiOx:Zn1-xCdxS can be used as an effective ETL and its band energy can be tuned by varying the TiOx:Zn1-xCdxS ratio. At the optimal ratio of 50:50 (vol%), the MAPbIxCl1-x perovskite and PCBTBT:PC70BM polymer solar cells achieved 9.79% and 4.95%, respectively. Morphological and optoelectronic analyses showed that tailoring band edges and homogeneous distribution of the local surface charges could improve the solar cells efficiency by more than 2%. We proposed a plausible mechanism to rationalize the variation in morphology and band energy of the ETL.

Corrosion Initiation and Propagation on Carburized Martensitic Stainless Steel Surfaces Studied via Advanced Scanning Probe Microscopy.

Historically, high carbon steels have been used in mechanical applications because their high surface hardness contributes to excellent wear performance. However, in aggressive environments, current bearing steels exhibit insufficient corrosion resistance. Martensitic stainless steels are attractive for bearing applications due to their high corrosion resistance and ability to be surface hardened via carburizing heat treatments. Here three different carburizing heat treatments were applied to UNS S42670: a high-temperature temper (HTT), a low-temperature temper (LTT), and carbo-nitriding (CN). Magnetic force microscopy showed differences in magnetic domains between the matrix and carbides, while scanning Kelvin probe force microscopy (SKPFM) revealed a 90⁻200 mV Volta potential difference between the two phases. Corrosion progression was monitored on the nanoscale via SKPFM and in situ atomic force microscopy (AFM), revealing different corrosion modes among heat treatments that predicted bulk corrosion behavior in electrochemical testing. HTT outperforms LTT and CN in wear testing and thus is recommended for non-corrosive aerospace applications, whereas CN is recommended for corrosion-prone applications as it exhibits exceptional corrosion resistance. The results reported here support the use of scanning probe microscopy for predicting bulk corrosion behavior by measuring nanoscale surface differences in properties between carbides and the surrounding matrix.

Charge-Trapping-Induced Non-Ideal Behaviors in Organic Field-Effect Transistors.

Organic field-effect transistors (OFETs) with impressively high hole mobilities over 10 cm2 V-1 s-1 and electron mobilities over 1 cm2 V-1 s-1 have been reported in the past few years. However, significant non-ideal electrical characteristics, e.g., voltage-dependent mobilities, have been widely observed in both small-molecule and polymer systems. This issue makes the accurate evaluation of the electrical performance impossible and also limits the practical applications of OFETs. Here, a semiconductor-unrelated, charge-trapping-induced non-ideality in OFETs is reported, and a revised model for the non-ideal transfer characteristics is provided. The trapping process can be directly observed using scanning Kelvin probe microscopy. It is found that such trapping-induced non-ideality exists in OFETs with different types of charge carriers (p-type or n-type), different types of dielectric materials (inorganic and organic) that contain different functional groups (OH, NH2 , COOH, etc.). As fas as it is known, this is the first report for the non-ideal transport behaviors in OFETs caused by semiconductor-independent charge trapping. This work reveals the significant role of dielectric charge trapping in the non-ideal transistor characteristics and also provides guidelines for device engineering toward ideal OFETs.