Conducting Probe Atomic Force Microscopy Research Articles

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.

CP-AFM Molecular Tunnel Junctions with Alkyl Backbones Anchored Using Alkynyl and Thiol Groups: Microscopically Different Despite Phenomenological Similarity.

In this paper, we report results on the electronic structure and transport properties of molecular junctions fabricated via conducting probe atomic force microscopy (CP-AFM) using self-assembled monolayers (SAMs) of n-alkyl chains anchored with acetylene groups (CnA; n = 8, 9, 10, and 12) on Ag, Au, and Pt electrodes. We found that the current-voltage (I-V) characteristics of CnA CP-AFM junctions can be very accurately reproduced by the same off-resonant single-level model (orSLM) successfully utilized previously for many other junctions. We demonstrate that important insight into the energy-level alignment can be gained from experimental data of transport (processed via the orSLM) and ultraviolet photoelectron spectroscopy combined with ab initio quantum chemical information based on the many-body outer valence Green's function method. Measured conductance GAg < GAu < GPt is found to follow the same ordering as the metal work function ΦAu < ΦAu < ΦPt, a fact that points toward a transport mediated by an occupied molecular orbital (MO). Still, careful data analysis surprisingly revealed that transport is not dominated by the ubiquitous HOMO but rather by the HOMO-1. This is an important difference from other molecular tunnel junctions with p-type HOMO-mediated conduction investigated in the past, including the alkyl thiols (CnT) to which we refer in view of some similarities. Furthermore, unlike in CnT and other junctions anchored with thiol groups investigated in the past, the AFM tip causes in CnA an additional MO shift, whose independence of size (n) rules out significant image charge effects. Along with the prevalence of the HOMO-1 over the HOMO, the impact of the "second" (tip) electrode on the energy level alignment is another important finding that makes the CnA and CnT junctions different. What ultimately makes CnA unique at the microscopic level is a salient difference never reported previously, namely, that CnA's alkyne functional group gives rise to two energetically close (HOMO and HOMO-1) orbitals. This distinguishes the present CnA from the CnT, whose HOMO stemming from its thiol group is well separated energetically from the other MOs.

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.

Gaining insight into molecular tunnel junctions with a pocket calculator without I-V data fitting. Five-thirds protocol.

The protocol put forward in the present paper is an attempt to meet the experimentalists' legitimate desire of reliably and easily extracting microscopic parameters from current-voltage measurements on molecular junctions. It applies to junctions wherein charge transport dominated by a single level (molecular orbital, MO) occurs via off-resonant tunneling. The recipe is simple. The measured current-voltage curve I = I(V) should be recast as a curve of V5/3/I versus V. This curve exhibits two maxima: one at positive bias (V = Vp+), another at negative bias (V = Vp-). The values Vp+ > 0 and Vp- < 0 at the two peaks of the curve for V5/3/I at positive and negative bias and the corresponding values Ip+ = I(Vp+) > 0 and Ip- = I(Vp-) < 0 of the current is all information needed as input. The arithmetic average of Vp+ and |Vp-| in volt provides the value in electronvolt of the MO energy offset ε0 = EMO - EF relative to the electrode Fermi level (|ε0| = e(Vp+ + |Vp-|)/2). The value of the (Stark) strength of the bias-driven MO shift is obtained as γ = (4/5)(Vp+ - |Vp-|)/(Vp+ + |Vp-|) sign (ε0). Even the low-bias conductance estimate, G = (3/8)(Ip+/Vp+ + Ip-/Vp-), can be a preferable alternative to that deduced from fitting the I-V slope in situations of noisy curves at low bias. To demonstrate the reliability and the generality of this "five-thirds" protocol, I illustrate its wide applicability for molecular tunnel junctions fabricated using metallic and nonmetallic electrodes, molecular species possessing localized σ and delocalized π electrons, and various techniques (mechanically controlled break junctions, STM break junctions, conducting probe AFM junctions, and large area junctions).

(Invited) Transparent Conductive Films of PEDOT:PSS-Amino Acid Composite

Transparent conductive electrode is an important component of optoelectronic devices such as light emitting diodes, photodiodes, and photovoltaic cells as well touchscreen technology. Growing demand for these technologies, as well as need for functionalities such as cost-effectiveness and flexibility, has resulted in various research on developing organic polymer-based transparent electrodes as an alternative to indium tin oxide (ITO) which is the current industry standard. One of the organic conducting polymers most commonly studied for their potential to be used as ITO-free transparent electrodes is PEDOT:PSS due to its high transmittance as a thin film, solution processability, flexibility, environmental stability, and commercial availability. There have been various works carried out to improve the conductivity of the PEDOT:PSS-based thin films by introducing dopants to improve the charge transport. We present our results demonstrating that not only the conductivity but also the transmittance of PEDOT-PSS-based films can be significantly improved by the introduction of amino acids such as phenylalanine in the film. We have observed that this enhancement in conductivity and optical transmittance of PEDOT:PSS-phenylalanine composite film is retained even when the amount of amino acid in the composite films is larger than the amount of PEDOT:PSS. We will present our study on the charge transport mechanism on these films based on electrochemical impedance spectroscopy (EIS) measurements. We will also further present our studies based on Scanning Electron Microscopy (SEM) as well as Scanning Probe Microscopy techniques such as topography imaging and conducting probe atomic force microscopy (CP-AFM) to elucidate the relationship between film morphology and charge transport in these composite films. The use of bioderived materials such as amino acids to create transparent composite films could open up avenues for developing and integrating bio-based materials in future electronics, help improve the environmental footprint of the electronics, and potentially also allow for the development of materials with a higher degree of biocompatibility for their application in bioelectronics.

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.

Exploring the Local Optoelectronic Properties of ALD Grown TiO2 Photoelectrode-Coatings with Atomic Force Microscopy Methods

Photoelectrochemical cells (PECs) hold great promise as an environmentally friendly method of converting sunlight into valuable fuels. However, the semiconductor components of PEC photoelectrodes are susceptible to corrosion under photoelectrochemical conditions.In order to protect the surface of these semiconductors from degradation, a thin overlayer of Titanium dioxide (TiO2) is often applied by atomic layer deposition (ALD). In addition to their protecting function, the physicochemical properties of these thin films significantly affect the overall performance of the device. The local nano-scale optoelectronic characteristics, which considerably influence their macroscopic properties, have rarely been reported in the literature.AFM methods constitute a powerful tool to investigate photo-induced charge separation, charge transport and recombination on photoelectrode surfaces with nanometer resolution.In this context, we have employed Tunneling Conductive AFM (TUNA) and Kelvin Probe Force Microscopy (KPFM) in the dark and under illumination to investigate the surface of ALD-grown TiO2. The synthesis conditions determine the morphology, which has a strong impact on the local optoelectronic properties. TUNA measurements reveal higher photogenerated currents on the grain and facet boundaries, showing that these regions can be favorable conduction pathways. Based on KPFM experiments we can quantify the more efficient photo-induced charge separation on the crystalline TiO2 inclusions, which generate a significant surface photopotential (~450 mV) upon UV-illumination. Categorization of different regions of surface topography based on morphology allows us to analyze the evolution of surface potential over time and extract localized time constants for carrier dynamic processes on the films. This spatially resolved information provides valuable insight to guide the development of macroscopically stable and efficient photoelectrodes through the engineering of microstructure at the nano scale.

(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.

Effect of Nitrogen Ion Diffusion Jumps in Nanometer-Sized Si3N4 Memristors Investigated by Low-Frequency Noise Spectroscopy

The elementary jumps in the electron current through conducting filaments of two nanometer-sized virtual memristor structures consisting of a contact of a conductive atomic force microscope probe to the Si3N4 layer with the thickness of 6[Formula: see text]nm deposited onto the [Formula: see text]-Si(001) conductive substrates are investigated. These structures are: (S1) the Si3N4/Si film; (S2) the Si3N4/SiO2/Si stack, a similar structure with 2[Formula: see text]nm SiO2 sublayer between the film and the substrate. Usually, such investigations are performed by the analysis of the waveform of this current with the aim of extracting the random telegraph noise (RTN). Here, we develop a new indirect method, which is based on the measurement of the spectrum of the low-frequency flicker noise in the current without extracting the RTN. We propose that the flicker noise is caused by the motion (drift/diffusion) of nitrogen ions via vacancies within and around the filament. The number of these ions is estimated by taking into account the geometrical parameters of the filament. This allows us to estimate the root mean square magnitude [Formula: see text] of the current jumps, which are caused by random jumps of nitrogen ions, and the number M of these ions. This is fundamental for understanding the elementary mechanisms of the electron current flowing through the filament and the resistive switching in memristor devices.

A multi-resistance wide-range calibration sample for conductive probe atomic force microscopy measurements.

Measuring resistances at the nanoscale has attracted recent attention for developing microelectronic components, memory devices, molecular electronics, and two-dimensional materials. Despite the decisive contribution of scanning probe microscopy in imaging resistance and current variations, measurements have remained restricted to qualitative comparisons. Reference resistance calibration samples are key to advancing the research-to-manufacturing process of nanoscale devices and materials through calibrated, reliable, and comparable measurements. No such calibration reference samples have been proposed so far. In this work, we demonstrate the development of a multi-resistance reference sample for calibrating resistance measurements in conductive probe atomic force microscopy (C-AFM) covering the range from 100 Ω to 100 GΩ. We present a comprehensive protocol for in situ calibration of the whole measurement circuit encompassing the tip, the current sensing device, and the system controller. Furthermore, we show that our developed resistance reference enables the calibration of C-AFM with a combined relative uncertainty (given at one standard deviation) lower than 2.5% over an extended range from 10 kΩ to 100 GΩ and lower than 1% for a reduced range from 1 MΩ to 50 GΩ. Our findings break through the long-standing bottleneck in C-AFM measurements, providing a universal means for adopting calibrated resistance measurements at the nanoscale in the industrial and academic research and development sectors.

Chirality Versus Symmetry: Electron's Spin Selectivity in Nonpolar Chiral Lead-Bromide Perovskites.

In the last decade, chirality-induced spin selectivity (CISS), the spin-selective electron transport through chiral molecules, has been described in a large range of materials, from insulators to superconductors. Because more experimental studies are desired for the theoretical understanding of the CISS effect, chiral metal-halide semiconductors may contribute to the field thanks to their chiroptical and spintronic properties. In this regard, this work uses new chiral organic cations S-HP1A and R-HP1A (HP1A = 2-hydroxy-propyl-1-ammonium) to prepare 2D chiral halide perovskites (HPs) which crystallize in the enantiomorphic space groups P43 21 2 and P41 21 2, respectively. The fourfold symmetry induces antiferroelectricity along the stacking axis which, combined to incomplete Rashba-like splitting in each individual 2D polar layer, results in rare spin textures in the band structure. As revealed by magnetic conductive-probe atomic force microscopy (AFM) measurements, these materials show CISS effect with partial spin polarization (SP; ±40-45%). This incomplete effect is efficient enough to drive a chiro-spintronic device as demonstrated by the fabrication of spin valve devices with magnetoresistance (MR) responses up to 250 K. Therefore, these stable lead-bromide HP materials not only represent interesting candidates for spintronic applications but also reveal the importance of polar symmetry-breaking topology for spin selectivity.

Bacterial extracellular electron transfer components are spin selective.

Metal-reducing bacteria have adapted the ability to respire extracellular solid surfaces instead of soluble oxidants. This process requires an electron transport pathway that spans from the inner membrane, across the periplasm, through the outer membrane, and to an external surface. Multiheme cytochromes are the primary machinery for moving electrons through this pathway. Recent studies show that the chiral-induced spin selectivity (CISS) effect is observable in some of these proteins extracted from the model metal-reducing bacteria, Shewanella oneidensis MR-1. It was hypothesized that the CISS effect facilitates efficient electron transport in these proteins by coupling electron velocity to spin, thus reducing the probability of backscattering. However, these studies focused exclusively on the cell surface electron conduits, and thus, CISS has not been investigated in upstream electron transfer components such as the membrane-associated MtrA, or periplasmic proteins such as small tetraheme cytochrome (STC). By using conductive probe atomic force microscopy measurements of protein monolayers adsorbed onto ferromagnetic substrates, we show that electron transport is spin selective in both MtrA and STC. Moreover, we have determined the spin polarization of MtrA to be ∼77% and STC to be ∼35%. This disparity in spin polarizations could indicate that spin selectivity is length dependent in heme proteins, given that MtrA is approximately two times longer than STC. Most significantly, our study indicates that spin-dependent interactions affect the entire extracellular electron transport pathway.

Unambiguous Measurement of Local Hole Current in Organic Semiconductors Using Conductive Atomic Force Microscopy

Conductive atomic force microscopy (C-AFM) is a widely used tool for studying the charge transport properties of organic semiconductor films with nanoscale resolution. Local hole current is commonly measured by electrically contacting the film with a high work function C-AFM probe on top and an underlying electrode coated with a hole transport layer. The two voltage polarities, corresponding to the probe injection and substrate injection of holes, are both found in the C-AFM literature; nevertheless, there has been a lack of consideration about the possible influence of voltage polarity on image contrast and charge transport mechanisms. By analyzing local hole current maps and current–voltage curves for three organic semiconductors (a small molecule and two polymers), we find that probe and substrate injection leads to drastically different hole current maps and charge transport mechanisms. Specifically, the substrate injection of holes exhibits ohmic characteristics at low voltages and space-charge-limited current behavior at elevated voltages. Conversely, the probe injection of holes leads to injection-limited current that is sensitive to the state of the probe–sample interface. These measurements provide a blueprint for ensuring that C-AFM measurements are unambiguously probing the bulk properties of organic semiconductor films.

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.

Molecular relays in nanometer-scale alumina: effective encapsulation 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 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 photoelectrodeposition 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 cm-2 (at ∼-0.32 V vs. Ag/AgCl) was measured, the highest reported for CsPbBr3 based aqueous photoelectrodes. This work demonstrates a way for stabilizing perovskite semiconductors in polar and protonic electrolytes as photoelectrodes for the generation of solar fuels.

Easily processable spin filters: exploring the chiral induced spin selectivity of bowl-shaped chiral subphthalocyanines.

High spin polarization (SP) in studies of chiral induced spin selectivity (CISS) is only observed when chiral molecules are properly organized. This is generally achieved by using anchoring groups or complex supramolecular polymers. A new class of spin filters based on bowl-shaped aromatics is reported, which form high-quality thin-films by simply spin-coating and displaying high spin filtering properties. In particular, we fabricate devices containing enantiopure tribromo-subphthalocyanines (SubPcs), and measure the CISS effect by means of magnetic conductive probe atomic force microscopy (mc-AFM). Circular dichroism and AFM experiments reveal that the resulting thin-film presents a well-ordered chiral structure. Remarkably, the resulting devices show SPs as high as ca. 50%, which are comparable to those obtained by using the current complex methodologies. These results boost the potential of bowl-shaped aromatics as easily processable spin filters, opening new frontiers toward realistic and efficient spintronic devices based on the CISS effect.

Enhancing the electrical properties of graphite nanoflake through gamma-ray irradiation

Understanding changes in material properties through external stimuli is critical to validating the expected performance of materials as well as engineering material properties in a controlled manner. Here, we investigate a change in the c-axis electrical properties of graphite nanoflakes (GnFs) induced by gamma-ray irradiation, using conductive probe atomic force microscopy (CP-AFM). The fundamentals behind the change in their electrical properties are elucidated by analyzing the interlayer spacing, graphitization, and morphology. An increase in gamma-ray irradiation dose for GnFs leads to an exponential increase in the electrical conductance and a gradual decrease in the interlayer spacing, while accompanying indistinguishable changes in their morphology. Our experimental results suggest that the c-axis electrical conductance enhancement of GnFs with gamma-ray irradiation might be attributed to a reduction in interlayer spacing, though the created defects may also play a role. This study demonstrates that gamma-ray irradiation can be a promising route to tailor the electrical properties of GnFs.

Band Bending and Ratcheting Explain Triboelectricity in a Flexoelectric Contact Diode.

Triboelectricity was recognized millennia ago, but the fundamental mechanism of charge transfer is still not understood. We have recently proposed a model where flexoelectric band bending due to local asperity contacts drives triboelectric charge transfer in non-metals. While this ab initio model is consistent with a wide range of observed phenomena, to date there have been no quantitative analyses of the proposed band bending. In this work we use a Pt0.8Ir0.2 conductive atomic force microscope probe to simultaneously deform a Nb-doped SrTiO3 sample and collect current-bias data. The current that one expects based upon an analysis including the relevant flexoelectric band bending for a deformed semiconductor quantitively agrees with the experiments. The analysis indicates a general ratcheting mechanism for triboelectric transfer and strong experimental evidence that flexoelectric band bending is of fundamental importance for triboelectric contacts.

Investigation of intrinsic charge transport via alkyl thiol molecular electronic junctions with conductive probe atomic force microscopy

Investigation of intrinsic charge transport via alkyl thiol molecular electronic junctions with conductive probe atomic force microscopy

Electric-Field-Assisted Contact Mode AFM-Based Nanolithography with Low Stiffness Conductive Probes

Abstract Electric-field-assisted atomic force microscope (E-AFM) nanolithography is a novel polymer-patterning technique that has diverse applications. E-AFM uses a biased AFM tip with conductive coatings to make patterns with little probe-sample interaction, which thereby avoids the tip wear that is a major issue for contact-mode AFM-based lithography, which usually requires a high probe-sample contact force to fabricate nanopatterns; however, the relatively large tip radius and large tip-sample separation limit its capacity to fabricate high-resolution nanopatterns. In this paper, we developed a contact mode E-AFM nanolithography approach to achieve high-resolution nanolithography of poly (methyl methacrylate) (PMMA) using a conductive AFM probe with a low stiffness (~0.16 N/m). The nanolithography process generates features by biasing the AFM probe across a thin polymer film on a metal substrate. A small constant force (0.5-1 nN) applied on the AFM tip helps engage the tip-film contact, which enhances nanomachining resolution. This E-AFM nanolithography approach enables high-resolution nanopatterning with feature width down to ~16 nm, which is less than one half of the nominal tip radius of the employed conductive AFM probes.