Conductive Atomic Force Microscopy Research Articles

Stripe noise removal in conductive atomic force microscopy

Conductive atomic force microscopy (c-AFM) can provide simultaneous maps of the topography and electrical current flow through materials with high spatial resolution and it is playing an increasingly important role in the characterization of novel materials that are being investigated for novel memory devices. However, noise in the form of stripe features often appear in c-AFM images, challenging the quantitative analysis of conduction or topographical information. To remove stripe noise without losing interesting information, as many as sixteen destriping methods are investigated in this paper, including three additional models that we propose based on the stripes characteristics, and thirteen state-of-the-art destriping methods. We have also designed a gradient stripe noise model and obtained a ground truth dataset consisting of 800 images, generated by rotating and cropping a clean image, and created a noisy image dataset by adding random intensities of simulated noise to the ground truth dataset. In addition to comparing the results of the stripe noise removal visually, we performed a quantitative image quality comparison using simulated datasets and 100 images with very different strengths of simulated noise. All results show that the Low-Rank Recovery method has the best performance and robustness for removing gradient stripe noise without losing useful information. Furthermore, a detailed performance comparison of Polynomial fitting and Low-Rank Recovery at different levels of real noise is presented.

Pt-Black-Modified (Hemi)spherical AFM Sensors: In Situ Imaging of Light-Driven Hydrogen Peroxide Evolution.

In this work, we present (hemi)spherical atomic force microscopy (AFM) sensors for the detection of hydrogen peroxide. Platinum-black (Pt-B) was electrodeposited onto conductive colloidal AFM probes or directly at recessed microelectrodes located at the end of a tipless cantilever, resulting in electrocatalytically active cantilever-based sensors that have a small geometric area but, due to the porosity of the films, exhibit a large electroactive surface area. Focused ion beam-scanning electron microscopy tomography revealed the porous 3D structure of the deposited Pt-B. Given the accurate positioning capability of AFM, these probes are suitable for local in situ sensing of hydrogen peroxide and at the same time can be used for (electrochemical) force spectroscopy measurements. Detection limits for hydrogen peroxide in the nanomolar range (LOD = 68 ± 7 nM) were obtained. Stability test and first in situ proof-of-principle experiments to achieve the electrochemical imaging of hydrogen peroxide generated at a microelectrode and at photocatalytically active structured poly(heptazine imide) films are demonstrated. Force spectroscopic data of the photocatalyst films were recorded in ambient conditions, in solution, and by applying a potential, which demonstrates the versatility of these novel Pt-B-modified spherical AFM probes.

High pressure induced formation of carbon nanorods from tetracosane

Morphology control of carbon structures is essential for improving their performance in many applications. Direct pyrolysis of organic precursors, however, usually yields bulk amorphous carbon. Therefore, traditional methods for controlling the morphology of carbon structures involve multistep processes and complex precursor molecules. While various methods have been developed under ambient pressure, the impact of pressure on the morphology of the resulting carbon structures remains unexplored. Herein, we present the synthesis of carbon nanorods by direct pyrolysis of the low-cost aliphatic hydrocarbon tetracosane under high pressure conditions. The diameters of the carbon nanorods are adjusted by simply varying the synthetic pressures. High pressure allows controlling both the nanorod morphology as well as the degree of order, and local conductivity of the thus prepared nanorods has been confirmed by conductive atomic force microscopy measurements. Our method promises a convenient strategy to synthesize carbon structures with controlled morphology and high ordered chemical structure, which opens opportunities for potential electronic and electrochemical applications.

Controlled Sixfold Symmetric Exfoliation of Oriented MoS2 Monolayers by Coulomb Force

AbstractAtoms, molecules, and nanoparticles can be spatially manipulated by an atomic force microscopy (AFM) tip, through van der Waals (vdW) and/or Coulomb forces. These point‐to‐point manipulations are highly accurate at nanoscale, facilitating the construction and modification of nanostructures. Nevertheless, it is difficult to manipulate 2D layers in vdW crystals by an AFM tip, because the tip‐induced attractive force is usually insufficient to outcompete the interlaminar vdW forces. Herein, manipulation of the surface layers on a MoS2 single crystal by a conductive AFM tip is successfully reported. By applying a bias between the tip and MoS2, the Coulomb attractive force allows the topmost MoS2 layers to be picked up. These exfoliated layers are deformed into micron‐sized bubbles with sixfold symmetry, which are composed of high‐quality monolayers and visually reflecting the hexagonal lattice orientation. The underlying mechanisms of the sixfold symmetric exfoliation and the formation of monolayers are discussed by in situ monitoring of the tunneling volt‐ampere characteristics and simulation of the force distribution. The findings open a new route to obtain high‐quality transition metal dichalcogenide (TMD) monolayers and their derived nanostructures on the surface of TMD single crystals for optoelectronic and photonic device applications.

Electrochemical Metallization Memristive Devices with Al Active Electrode Using Engineered Mixed Hexagonal/Orthorhombic Polycrystalline YMnO3

We report electrochemical metallization (ECM) resistive switching in polycrystalline YMnO3 memristive devices using Al as an active electrode. Al/YMnO3/Pt devices exhibit bipolar resistive switching with a high ROFF/RON ratio of 104, low operational voltages of VSet ≈ 1.7 V and VReset ≈ −0.36 V and good retention properties. The resistive switching is intimately linked to the coexistence of the orthorhombic and hexagonal YMnO3 phases. The characterization of these two nanocrystalline phases is realized not only by X‐ray diffraction – which is shown to be unable to reveal the presence of the orthorhombic phase – but also by a set of correlative microscopy and spectroscopy methods (scanning electron microscopy, optical microscopy, Raman spectroscopy and conductive atomic force microscopy). The origin of resistive switching is ascribed to an Al filament‐based electrochemical metallization mechanism that likely occurs along an oxygen‐deficient grain boundary between the hexagonal and orthorhombic nanocrystalline YMnO3 phases. The unique microstructure provided by the mixed polycrystalline phase films allows to use Al as an active electrode in YMnO3‐based ECM cells, and gives perspective for further miniaturization of the devices.

Towards quantification of doping in gallium arsenide nanostructures by low-energy scanning electron microscopy and conductive atomic force microscopy.

We calculate a universal shift in work function of 59.4 meV per decade of dopant concentration change that applies to all doped semiconductors and from this use Monte Carlo simulations to simulate the resulting change in secondary electron yield for doped GaAs. We then compare experimental images of doped GaAs layers from scanning electron microscopy and conductive atomic force microscopy. Kelvin probe force microscopy allows to directly measure and map local work function changes, but values measured are often smaller, typically only around half, of what theory predicts for perfectly clean surfaces.

Impact of Non‐Stoichiometric Phases and Grain Boundaries on the Nanoscale Forming and Switching of HfOx Thin Films

AbstractHfO2 is one of the most common memristive materials and it is widely accepted that oxygen vacancies are prerequisite to reduce the forming voltage of the respective memristive devices. Here, a series of six oxygen engineered substoichiometric HfO2 − x thin films with varying oxygen deficiency is investigated by conductive atomic force microscopy (c‐AFM) and the switching process of substoichiometric films is observed on the nanoscale. X‐ray diffractometry (XRD) exhibits a phase transition from stoichiometric, monoclinic HfO2 toward oxygen deficient, rhombohedral HfO1.7. The conductance of HfO2 − x is increasing with increasing oxygen deficiency, which is consistent with the increasing prevalence of the highly conductive rhombohedral phase. Simultaneously, c‐AFM reveals significant local conductivity differences between grains and grain boundaries, regardless of the level of oxygen deficiency. Single grains of highly oxygen deficient samples are formed at significant lower voltages. The mean forming voltage is reduced from (7.0 ± 0.6) V for HfO2 to (1.9 ± 0.8) V for HfO1.7. Resistive switching on the nanoscale is established for single grains for the highest deficient thin film samples. The final resistance state is thereby dependent on the initial conductivity of the grains. These studies offer valuable insights into the switching behavior of memristive polycrystalline HfO2.

Simultaneous Visualization of Microscopic Conductivity and Deformation in Conductive Elastomers.

Conductive elastomers are promising for a wide range of applications in many fields due to their unique mechanical and electrical properties, and an understanding of the conductive mechanisms of such materials under deformation is crucial. However, revealing the microscopic conduction mechanism of conductive elastomers is a challenge. In this study, we developed a method that combines in situ deformation nanomechanical atomic force microscopy (AFM) and conductive AFM to successfully and simultaneously characterize the microscopic deformation and microscopic electrical conductivity of nanofiller composite conductive elastomers. With this approach, we visualized the conductive network structure of carbon black and carbon nanotube composite conductive elastomers at the nanoscale, tracked their microscopic response under different compressive strains, and revealed the correlation between microscopic and macroscopic electrical properties. This technique is important for understanding the conductive mechanism of conductive elastomers and improving the design of conductive elastomers.

In Operando Near‐Field Optical Investigation of Memristive Ta2O5 Thin Film Devices with a Graphene Top Electrode

AbstractResistive switching devices based on metal oxides are candidates for nonvolatile memory storage. They often rely on the valence change mechanism, the field‐induced movement of donor ions leading to nanoscale conductive paths in filamentary‐type devices. Devices usually consist of a transition metal oxide like Ta2O5 sandwiched between two metal electrodes. Critical parameters of the devices, such as cycle‐to‐cycle variability, Roff/Ron ratio, and endurance depend on the morphology and composition of the filaments. However, investigating filaments on the nanoscale is cumbersome, and commonly applied techniques such as conductive atomic force or transmission electron microscopy require delaminating the metal top electrode, inhibiting in operando investigations over many switching cycles. Here, the authors use infrared scattering‐type scanning near‐field optical microscopy (s‐SNOM) to investigate resistive switching in Ta2O5 films with a graphene top electrode in operando and reveal individual filaments on the device level. By selecting an appropriate illumination frequency, the authors can trace the evolution of filaments and the joule heating‐induced retraction of the top electrode until device failure. s‐SNOM promises a deeper understanding of resistive switching devices’ microscopic switching behavior and applies to a wide range of resistive switching oxides, such as HfO2, SrTiO3, and SiO2.

Atomically thin MXene/WSe2 Schottky heterojunction towards enhanced photogenerated charge carrier

Two-dimensional materials garner increasing interest in next-generation electronics and optoelectronic devices due to their atomic-thin nature and distinctive physical properties. Building on these advances, we present the successful synthesis of a heterostructure composed of the semi-metallic Ti3C2-MXene and the semiconducting WSe2, in which the atomic layers are vertically aligned. The wet impregnation method effectively synthesizes an atomically thin Ti3C2-MXene/WSe2 heterostructure characterized by atomic force microscopy, Raman and time-resolved photoluminescence (TRPL) analysis. In addition, the current–voltage characteristics at the heterostructure reveal the Schottky junction probed by the scanning tunnelling microscopy and the conductive atomic force microscopy tip. The Schottky heterojunction also exhibits enhanced photocatalytic properties by improving the photogenerated charge carriers and inhibiting recombination. This work demonstrates the unique 2D–2D Ti3C2-MXene/WSe2 vertical heterojunction possesses superior photon trapping ability and can efficiently transport photogenerated charge carriers to the reaction sites to enhance photocatalysis performance.

Charge-carrier-concentration inhomogeneities in alkali-treated Cu(In,Ga)Se2 revealed by conductive atomic force microscopy tomography

Charge-carrier-concentration inhomogeneities in alkali-treated Cu(In,Ga)Se2 revealed by conductive atomic force microscopy tomography

Colloidal pathways of amorphous calcium carbonate formation lead to distinct water environments and conductivity.

CaCO3 is the most abundant biomineral and a major constituent of incrustations arising from water hardness. Polycarboxylates play key roles in controlling mineralization. Herein, we present an analytical and spectroscopic study of polycarboxylate-stabilized amorphous CaCO3 (ACC) and its formation via a dense liquid precursor phase (DLP). Polycarboxylates facilitate pronounced, kinetic bicarbonate entrapment in the DLP. Since bicarbonate is destabilized in the solid state, DLP dehydration towards solid ACC necessitates the formation of locally calcium deficient sites, thereby inhibiting nucleation. Magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy of poly-aspartate-stabilized ACC reveals the presence of two distinct environments. The first contains immobile calcium and carbonate ions and structural water molecules, undergoing restricted, anisotropic motion. In the second environment, water molecules undergo slow, but isotropic motion. Indeed, conductive atomic force microscopy (C-AFM) reveals that ACC conducts electrical current, strongly suggesting that the mobile environment pervades the bulk of ACC, with dissolved hydroxide ions constituting the charge carriers. We propose that the distinct environments arise from colloidally stabilized interfaces of DLP nanodroplets, consistent with the pre-nucleation cluster (PNC) pathway.

Multifunctional chemical anchors achieve a boosted fill factor and mitigate ion migration of high-stability perovskite solar cells.

To date, it is urgent to produce perovskite films with comparative or even better morphologies in an open-air environment. Unfortunately, a substantial number of trap states on the grain surface, especially the grain boundaries (GBs) of a perovskite layer, can bring about significant deterioration in the performance of PSCs. Trap-induced carrier recombination directly exerts a detrimental influence on the carrier collection efficiency and electronic properties of a perovskite active film. Herein, 4(5)-iodoimidazole (4II), a small organic molecule agent, was introduced to passivate the surface and bulk traps of the active film, which resulted in a controlled morphology, improved carrier extraction and suppressed ion migration for the devices fabricated in a relatively humid and O2-containing environment. Conductive atomic force microscopy (C-AFM) and Kelvin probe force microscopy (KPFM) measurements were applied to study trap passivation and suppression of ion migration across the GBs of perovskite films. The results manifest that the -CN group preferably bonds with the less-coordinated Pb2+ and the -NH- group favorably forms hydrogen bonds with the uncoordinated I-. As a result, the champion device delivered a significantly boosted power conversion efficiency from 17.22% to 20.95%, with an improved fill factor (FF) from 70.54% to 80.40%, and improved ambient stability of the unencapsulated device. This study may probe research insight into the design of passivators with synergistic effects for morphology control and reduction of carrier recombination loss for equally efficient perovskite photovoltaics fabricated in ambient air.

Enhancing electrocatalytic activity in metallic thin films through surface segregation of carbon.

Thin layers of commonly used adhesion metals i.e., Cr and Ti were annealed to investigate and estimate their impact on the electrochemical properties of the carbon nanomaterials grown on top of them. The microstructure, surface chemistry, and electrochemical activities of these materials were evaluated and compared with those of as-deposited thin films. The results from X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, grazing incidence X-ray diffraction (GIXRD), time-of-flight elastic recoil detection analysis (TOF-ERDA), and conductive atomic force microscopy (C-AFM) indicated the formation of a catalytic graphite layer on Cr following annealing, while no such layer was formed on Ti. This is attributed to the formation of the Cr2O3 layer on annealed Cr, which acts as a barrier to carbon diffusion into the underlying Cr. Conversely, Ti exhibits a high solubility for both carbon and oxygen, preventing the formation of the graphite layer. Cyclic voltammetry results showed that annealed Cr electrodes are electrochemically active towards both dopamine (DA) and ascorbic acid (AA) while no electrochemical activity is exhibited by annealed Ti. Quantum chemical calculations suggested that the presence of carbon as graphene or an amorphous form is critical for the oxidation reaction of probes. These results are significant for comprehending how the distinct solubilities of typical interstitial solutes influence the microstructure of adhesion metal layers and consequently yield diverse electrochemical properties.

Alleviating nanostructural phase impurities enhances the optoelectronic properties, device performance and stability of cesium-formamidinium metal-halide perovskites.

The technique of alloying FA+ with Cs+ is often used to promote structural stabilization of the desirable α-FAPbI3 phase in halide perovskite devices. However, the precise mechanisms by which these alloying approaches improve the optoelectronic quality and enhance the stability have remained elusive. In this study, we advance that understanding by investigating the effect of cationic alloying in CsxFA1-xPbI3 perovskite thin-films and solar-cell devices. Selected-area electron diffraction patterns combined with microwave conductivity measurements reveal that fine Cs+ tuning (Cs0.15FA0.85PbI3) leads to a minimization of stacking faults and an increase in the photoconductivity of the perovskite films. Ultra-sensitive external quantum efficiency, kelvin-probe force microscopy and photoluminescence quantum yield measurements demonstrate similar Urbach energy values, comparable surface potential fluctuations and marginal impact on radiative emission yields, respectively, irrespective of Cs content. Despite this, these nanoscopic defects appear to have a detrimental impact on inter-grains'/domains' carrier transport, as evidenced by conductive-atomic force microscopy and corroborated by drastically reduced solar cell performance. Importantly, encapsulated Cs0.15FA0.85PbI3 devices show robust operational stability retaining 85% of the initial steady-state power conversion efficiency for 1400 hours under continuous 1 sun illumination at 35 °C, in open-circuit conditions. Our findings provide nuance to the famous defect tolerance of halide perovskites while providing solid evidence about the detrimental impact of these subtle structural imperfections on the long-term operational stability.

Large area arrays of discrete single-molecule junctions derived from host-guest complexes.

The desire to continually reduce the lower limits of semiconductor integrated circuit (IC) fabrication methods continues to inspire interest in unimolecular electronics as a platform technology for the realization of future (opto)electronic devices. However, despite successes in developing methods for the construction and measurement of single-molecule and large-area molecular junctions, exercising control over the precise junction geometry remains a significant challenge. Here, host-guest complexes of the wire-like viologen derivative 1,1'-bis(4-(methylthio)-phenyl)-[4,4'-bipyridine]-1,1'-diium chloride ([1][Cl]2) and cucurbit[7]uril (CB[7]) have been self-assembled in a regular pattern over a gold substrate. Subsequently, ligandless gold nanoparticles (AuNPs) synthesized in situ are deposited over the host-guest array. The agreement between the conductance of individual mono-molecular junctions, appropriately chosen as a function of the AuNP diameter, within this array determined by conductive probe atomic force microscope (c-AFM) and true single-molecule measurements for a closely similar host-guest complex within a scanning tunneling microscope break-junction (STM-BJ) indicates the formation of molecular junctions derived from these host-guest complexes without deleterious intermolecular coupling effects.

Tilt‐Engineered Molecular‐Scale Selector for Enhanced Learning in Artificial Neural Networks

AbstractMiniaturization of individual selectors in crossbar‐array‐based artificial neural networks is essential for the advancement of the underlying neuromorphic electronics, as it improves learning, recognition, and prediction accuracies. This study proposes a tilt‐engineered molecular‐scale selector comprising a heterostructure of biphenyl‐4‐thiol (OPT2) or 1‐octanethiol (C8) molecular layers and an n‐type two‐dimensional MoS2 monolayer (1L‐MoS2) at an approximate contact radius of 3 nm, which is evaluated via conductive atomic force microscopy under various tip‐loading forces. The molecular tilt configuration controlled by the tip‐loading force is used as a rectifying engineer for the OPT2/1L‐MoS2 and C8/1L‐MoS2 heterojunction accuracies. Rectification ratios and conductance levels are significantly influenced by the molecular backbones and tilt angle. The proposed tilt‐engineered selector can aid in controlling undesired neural signals affecting vector–matrix multiplications and adjusting the switching range compatibility of an integrated synaptic device cell, significantly influencing the pattern recognition accuracy. By controlling the tilt angle, the recognition accuracy on the MNIST dataset increases from 78.65% to 86.45% and from 7.74% to 86.09% when using the OPT2/1L‐MoS2 and C8/1L‐MoS2 selector, respectively. The proposed molecular tilt configuration can be used for developing customized molecular‐scale selectors for crossbar‐array‐based artificial neural networks to improve learning while suppressing undesired neural signals.

Interface Engineering for Highly Efficient Perovskite Photovoltaics

In the past decade, major progress has taken place in the field of metal halide perovskite photovoltaics (PV), as witnessed by the recently achieved conversion efficiency of 25.7% [1] and the concrete opportunity to go beyond the thermodynamic limit of single junction PV by means of perovskite/ crystalline silicon tandems, with the very recent record of 33.2% [2]. Among the most recent efforts towards further development of perovskite PV and subsequent commercialization, strategies ranging from perovskite surface passivation and compositional engineering to thin film encapsulation, contribute to suppress the perovskite absorber and device instability to moisture ingress. In parallel, research efforts presently investigate the role of inorganic charge transport layers (CTLs) next to the one of the most commonly used organic CTLs, such as poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine (PTAA), [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) or C60. The inorganic layers are acknowledged to impart thermal and mechanical stability to the device, as well as to improve device efficiency yield.In this contribution, our recent research on atomic layer deposited (ALD) selective CTLs for metal halide perovskite PV [3] is reviewed by addressing two case studies, namely, SnO2 thin films, selective towards electron transport, and NiO thin films, selective towards hole transport. ALD is selected as deposition technology because of its merit of ultimate control over film thickness and conformality.ALD SnO2 [4]. based on cycles of tetrakis(dimethylamido)-tin and H2O as precursor and co-reactant, respectively, is the state-of-the art in both p-i-n perovskite single junction as well as tandem perovskite/crystalline silicon and perovskite/CIGS PV. Its presence is key to the device thermal and mechanical stability, to prevent humidity ingress in the device and suppress damage to the fullerene (PCBM or C60) during the sputtering of the transparent front contact. Moreover, SnO2 plays a key role in perovskite/perovskite tandem PV, where it serves as solvent barrier to prevent damage of the wide-band gap perovskite sub-cell during solution processing of the narrow-band gap perovskite top cell. In parallel, our in situ studies by means of IR spectroscopy during ALD of SnO2 on perovskite/fullerene disclose the reason behind the difference in device conversion efficiency when SnO2 is processed either on PCBM or C60, i.e. the devices based on PCBM underperform those based on C60 by 3% absolute difference. Specifically, the Sn-precursor is responsible for the modification of the ester group in PCBM thereby affecting the PCBM/perovskite interface and device efficiency.ALD NiO thin (7 nm) films [5], based on cycles of bis(methylcyclopentadienyl)nickel and H2O as precursor and co-reactant, respectively, are found to impart stability to the perovskite device under acceleration test at 85°C, with 80% retention of the initial conversion efficiency after 300 hours at 1 sun illumination. At the same time, the presence of the phosphonic acid-based self-assembled monolayer (SAM), is essential to engineer an almost lossless (i.e., in terms of suppression of charge recombination) NiO/SAM/perovskite interface. Also, the SAM homogeneity and surface coverage on NiO improve with respect to direct SAM processing on ITO (see figure), as witnessed by transmission electron microscopy (TEM) and conductive atomic force microscopy. This result is explained in terms of chemisorption reactions between SAM phosphonic acid groups and NiO hydroxyl groups. The SAM homogeneity on NiO leads to higher shunt resistance in the device with respect to the one with SAM directly processed on ITO. Finally, the combination of NiO and SAM results in a narrower distribution of device performance reaching more than 20% efficient champion device. In parallel, two-terminal perovskite/crystalline silicon tandem devices with an ITO/NiO/SAM tunnel recombination junction (TRJ) exhibit a better device yield with respect to tandem devices with an ITO/SAM TRJ, i.e. the standard deviation decreases from 4.6% with ITO/SAM to 2.0% with ITO/NiO/SAM.[1] Green et al., Prog. Photovolt. Res. Appl. 30, 687 (2022)[2] https://www.kaust.edu.sa/news/kaust-team-sets-world-record-for-tandem-solar-cell-efficiency[3] Zardetto et al., Sustainable Energy & Fuels 1, 30 (2017)[4] Bracesco et al., J. Vac. Sci. Technol. A, 38(6), 063206-1 (2020)[5] Phung et al., ACS Applied Materials and Interfaces. 14(1), 2166 (2022)[6] Phung et al., submitted to Sol. Mat. (2023) Figure 1

Molecular Relays in Nanometer Scale Alumina: Effective Protection Layers for Water-Submersed Halide Perovskite Photocathodes

Halide perovskite (HaP) solar cells have an excellent voltage efficiency (>70%) and a low electron-affinity conduction band minimum, making them prospective candidates to be used as photocathodes in integrated low-cost solar fuel generators. However, halide perovskites are notoriously unstable in aqueous solutions and immediately dissolve upon exposure to liquid water. Ultrathin layers (< 10 nm) of Al2O3 deposited by atomic layer deposition are suitable encapsulants to prevent water ingression but are also electronically insulating. Embedding linear conjugated organic molecules (‘molecular relays’) that transverse the insulating layer enables selective electron transport across the insulating encapsulating layer. The electronic functionality of the embedded molecular relays is verified by conductive probe atomic force microscopy and photo-electrodeposition of metal particles (Pt and Ag) from ethanolic solutions. Lastly, the encapsulated HaP photoelectrodes were submersed in a CO2-saturated aqueous electrolyte and a photocurrent of ~100 µA/cm2 (at ~ -0.32 V vs. Ag/AgCl) was measured. This work demonstrates a way for stabilizing semiconductors in polar and protonic electrolytes as photoelectrodes for the generation of solar fuels.

(Invited) Advanced Scanning Probe Microscopy for Studying Biofilm Formation and Single Cell Entities at Electrified Interfaces

Advanced scanning probe microscopy techniques such as atomic force – scanning electrochemical microscopy (AFM-SECM) und scanning electrochemical microscopy (SECM) are highly attractive hybrid techniques for studying biomedically relevant samples down to the single entity level. Our group introduced a new type of AFM-SECM probe having a conductive colloid instead of a sharp AFM tip. As this spherical microelectrode, which is located at the end of an electrically insulated AFM cantilever can be easily modified by electrodeposition with e.g., conductive polymers and electrocatalytic layers, single cell force spectroscopy under potential control allows studying adhesion properties [1,2]. Cell adhesion is a crucial parameter not only for developing new materials serving as substrates for neural scaffolds, electrodes, and biomedical devices but also in biofilm formation. Biofilms are well-organized aggregates of bacteria able to attach to and proliferate at almost every type of solid surface resulting in increased resistance to conventional antimicrobial and antibiofouling agents [3].The first attachment of bacterials is a process highly influenced by the nature of the surface, such as hydrophobicity, chemical structure, surface charge, and presence of antimicrobials [4].In this contribution, we present the potential of various scanning probe microscopy techniques, as suitable tools to locally investigate the early stages of biofilm formation and the effects of various antibiofouling and antimicrobial systems against Escherichia coli and Pseudomonas fluorescens. For example, the properties of polydopamine, a bio-compatible polymer, are studied in respect to early stages of bacterial adhesion in dependence of surface charge density and applied potential [5]. Colloidal conductive AFM probes can also be modified electrocatalytic layers, suitable for detecting signaling molecules and at the same time allow electrochemical force spectroscopy at soft samples like biomedically relevant single entities.