Spatially resolved random telegraph fluctuations of a single trap at the Si/SiO2 interface.

We use electrostatic force microscopy to spatially resolve random telegraph noise at the Si/SiO2 interface. Our measurements demonstrate that two-state fluctuations are localized at interfacial traps, with bias-dependent rates and amplitudes. These two-level systems lead to correlated carrier number and mobility fluctuations with a range of characteristic timescales; taken together as an ensemble, they give rise to a [Formula: see text] power spectral trend. Such individual defect fluctuations at the Si/SiO2 interface impair the performance and reliability of nanoscale semiconductor devices and will be a significant source of noise in semiconductor-based quantum sensors and computers. The fluctuations measured here are associated with a four-fold competition of rates, including slow two-state switching on the order of seconds and, in one state, fast switching on the order of nanoseconds which is associated with energy loss.

Spatially Resolved Dielectric Loss at the Si/SiO_{2} Interface.

The Si/SiO_{2} interface is populated by isolated trap states that modify its electronic properties. These traps are of critical interest for the development of semiconductor-based quantum sensors and computers, as well as nanoelectronic devices. Here, we study the electric susceptibility of the Si/SiO_{2} interface with nm spatial resolution using frequency-modulated atomic force microscopy. The sample measured here is a patterned dopant delta layer buried 2 nm beneath the silicon native oxide interface. We show that charge organization timescales of the Si/SiO_{2} interface range from 1-150 ns, and increase significantly around interfacial traps. We conclude that under time-varying gate biases, dielectric loss in metal-insulator-semiconductor capacitor devices is in the frequency range of MHz to sub-MHz, and is highly spatially heterogeneous over nm length scales.

Nanoscale force sensing of an ultrafast nonlinear optical response.

The nonlinear optical response of a material is a sensitive probe of electronic and structural dynamics under strong light fields. The induced microscopic polarizations are usually detected via their far-field light emission, thus limiting spatial resolution. Several powerful near-field techniques circumvent this limitation by employing local nanoscale scatterers; however, their signal strength scales unfavorably as the probe volume decreases. Here, we demonstrate that time-resolved atomic force microscopy is capable of temporally and spatially resolving the microscopic, electrostatic forces arising from a nonlinear optical polarization in an insulating dielectric driven by femtosecond optical fields. The measured forces can be qualitatively explained by a second-order nonlinear interaction in the sample. The force resulting from this nonlinear interaction has frequency components below the mechanical resonance frequency of the cantilever and is thus detectable by regular atomic force microscopy methods. The capability to measure a nonlinear polarization through its electrostatic force is a powerful means to revisit nonlinear optical effects at the nanoscale, without the need for emitted photons or electrons from the surface.

High Osmotic Power Generation via Nanopore Arrays in Hybrid Hexagonal Boron Nitride/Silicon Nitride Membranes.

Nanopores embedded in two-dimensional (2D) nanomaterials are a promising emerging technology for osmotic power generation. Here, coupling our new AFM-based pore fabrication approach, tip-controlled local breakdown (TCLB), with a hybrid membrane formed by coating silicon nitride (SiN) with hexagonal boron nitride (hBN), we show that high osmotic power density can be obtained in systems that do not possess the thinness of atomic monolayers. In our approach, the high osmotic performance arises from charge separation induced by the highly charged hBN surface rather than charge on the inner pore wall. Moreover, exploiting TCLB's capability of producing sub 10 nm pore arrays, we investigate the effects of pore-pore interaction on the overall power density. We find that an optimum pore-to-pore spacing of ∼500 nm is required to maintain an efficient selective transport mechanism.

The Effect of Photoinduced Surface Oxygen Vacancies on the Charge Carrier Dynamics in TiO2 Films.

Metal-oxide semiconductors (MOS) are widely utilized for catalytic and photocatalytic applications in which the dynamics of charged carriers (e.g., electrons, holes) play important roles. Under operation conditions, photoinduced surface oxygen vacancies (PI-SOV) can greatly impact the dynamics of charge carriers. However, current knowledge regarding the effect of PI-SOV on the dynamics of hole migration in MOS films, such as titanium dioxide, is solely based upon volume-averaged measurements and/or vacuum conditions. This limits the basic understanding of hole-vacancy interactions, as they are not capable of revealing time-resolved variations during operation. Here, we measured the effect of PI-SOV on the dynamics of hole migration using time-resolved atomic force microscopy. Our findings demonstrate that the time constant associated with hole migration is strongly affected by PI-SOV, in a reversible manner. These results will nucleate an insightful understanding of the physics of hole dynamics and thus enable emerging technologies, facilitated by engineering hole-vacancy interactions.

How high is a MoSe2monolayer?

Transition metal dichalcogenides (TMDCs) have attracted significant attention for optoelectronic, photovoltaic and photoelectrochemical applications. The properties of TMDCs are highly dependent on the number of stacked atomic layers, which is usually counted post-fabrication, using a combination of optical methods and atomic force microscopy height measurements. Here, we use photoluminescence spectroscopy, Raman spectroscopy, and three different AFM methods to demonstrate significant discrepancies in height measurements of exfoliated MoSe2flakes on SiO2depending on the method used. We also highlight the often overlooked effect that electrostatic forces can be misleading when measuring the height of a MoSe2flake using AFM.

Ergodic and Nonergodic Dynamics of Oxygen Vacancy Migration at the Nanoscale in Inorganic Perovskites.

Perovskites are widely utilized either as a primary component or as a substrate in which the dynamics of charged oxygen vacancy defects play an important role. Current knowledge regarding the dynamics of vacancy mobility in perovskites is solely based upon volume- and/or time-averaged measurements. This impedes our understanding of the basic physical principles governing defect migration in inorganic materials. Here, we measure the ergodic and nonergodic dynamics of vacancy migration at the relevant spatial and temporal scales using time-resolved atomic force microscopy techniques. Our findings demonstrate that the time constant associated with oxygen vacancy migration is a local property and can change drastically on short length and time scales, such that nonergodic states lead to a dramatic increase in the migration barrier. This correlated spatial and temporal variation in oxygen vacancy dynamics can extend hundreds of nanometers across the surface in inorganic perovskites.

Quantifying bio-filament morphology below the diffraction limit of an optical microscope using out-of-focus images.

A method to measure the dimensions of objects below the optical diffraction limit using diffraction analysis of out-of-focus bright-field images is presented. The method relies on the comparison of the diffraction patterns of an object of unknown size to those of calibration objects of known size. Correlative scanning electron microscope measurements are used to demonstrate the applicability of this method to measure 100 nm microbeads as well as objects with a geometry different from the calibration objects. This technique is important in the context of tethered particle experiments, in which bio-filaments are bound between a substrate and a microbead. This procedure is applied to obtain the diameters of axonal extensions or neurites that are mechanically created in samples of rat hippocampal neurons. The dependence of neurite geometry on mechanical pull speed is investigated, and the diameter is found to be rate independent.

Fully Quantized Electron Transfer Observed in a Single Redox Molecule at a Metal Interface.

Long-range electron transfer is a ubiquitous process that plays an important role in electrochemistry, biochemistry, organic electronics, and single molecule electronics. Fundamentally, quantum mechanical processes, at their core, manifest through both electron tunneling and the associated transition between quantized nuclear vibronic states (intramolecular vibrational relaxation) mediated by electron-nuclear coupling. Here, we report on measurements of long-range electron transfer at the interface between a single ferrocene molecule and a gold substrate separated by a hexadecanethiol quantum tunneling barrier. These redox measurements exhibit quantized nuclear transitions mediated by electron-nuclear coupling at 4.7 K in vacuum. By detecting the electric force associated with redox events by atomic force microscopy (AFM), with increasing AFM oscillation amplitude, the intensity of the observed  cantilever resonance frequency shift peak increases and then exhibits a series of discrete steps that are indicative of quantized nuclear transitions. The observed peak shapes agree well with a single-electron tunneling model with quantized nuclear state transitions associated with the conversion of the molecule between oxidized and reduced electronic states. This technique opens the door to simultaneously investigating quantized electron and nuclear dynamics in a diverse range of systems.

Amplitude Dependence of Resonance Frequency and its Consequences for Scanning Probe Microscopy.

With recent advances in scanning probe microscopy (SPM), it is now routine to determine the atomic structure of surfaces and molecules while quantifying the local tip-sample interaction potentials. Such quantitative experiments using noncontact frequency modulation atomic force microscopy is based on the accurate measurement of the resonance frequency shift due to the tip-sample interaction. Here, we experimentally show that the resonance frequency of oscillating probes used for SPM experiments change systematically as a function of oscillation amplitude under typical operating conditions. This change in resonance frequency is not due to tip-sample interactions, but rather due to the cantilever strain or geometric effects and thus the resonance frequency is a function of the oscillation amplitude. Our numerical calculations demonstrate that the amplitude dependence of the resonance frequency is an additional yet overlooked systematic error source that can result in nonnegligible errors in measured interaction potentials and forces. Our experimental results and complementary numerical calculations reveal that the frequency shift due to this amplitude dependence needs to be corrected even for experiments with active oscillation amplitude control to be able to quantify the tip-sample interaction potentials and forces with milli-electron volt and pico-Newton resolutions.

Relating Franck-Condon blockade to redox chemistry in the single-particle picture.

In this work, we explore Franck-Condon blockade in the "redox limit," where nuclear relaxation processes occur much faster than the rate of electron transfer. To this end, the quantized rate expressions for electron transfer are recast in terms of a quantized redox density of states (DOS) within a single phonon mode model. In the high temperature regime, this single-particle picture formulation of electron transfer is shown to agree well with the semi-classical rate and DOS expressions developed by Gerischer and Hopfield. Upon incorporation into a two electrode formulation, utilizing the master equation approach, the low temperature quantized conductance features of Franck-Condon blockade are reproduced. Moreover, at sufficiently large reorganization energies, it is argued that Franck-Condon blockade should also be observable in room temperature systems. In general, this work aims to further bridge descriptions of electron transfer and transport in the single-particle picture.

Measuring Spatially Resolved Collective Ionic Transport on Lithium Battery Cathodes Using Atomic Force Microscopy.

One of the main challenges in improving fast charging lithium-ion batteries is the development of suitable active materials for cathodes and anodes. Many materials suffer from unacceptable structural changes under high currents and/or low intrinsic conductivities. Experimental measurements are required to optimize these properties, but few techniques are able to spatially resolve ionic transport properties at small length scales. Here we demonstrate an atomic force microscope (AFM)-based technique to measure local ionic transport on LiFePO4 to correlate with the structural and compositional analysis of the same region. By comparing the measured values with density functional theory (DFT) calculations, we demonstrate that Coulomb interactions between ions give rise to a collective activation energy for ionic transport that is dominated by large phase boundary hopping barriers. We successfully measure both the collective activation energy and the smaller single-ion bulk hopping barrier and obtain excellent agreement with values obtained from our DFT calculations.

Rapid Mechanically Controlled Rewiring of Neuronal Circuits.

CNS injury may lead to permanent functional deficits because it is still not possible to regenerate axons over long distances and accurately reconnect them with an appropriate target. Using rat neurons, microtools, and nanotools, we show that new, functional neurites can be created and precisely positioned to directly (re)wire neuronal networks. We show that an adhesive contact made onto an axon or dendrite can be pulled to initiate a new neurite that can be mechanically guided to form new synapses at up to 0.8 mm distance in <1 h. Our findings challenge current understanding of the limits of neuronal growth and have direct implications for the development of new therapies and surgical techniques to achieve functional regeneration. Significance statement: Brain and spinal cord injury may lead to permanent disability and death because it is still not possible to regenerate neurons over long distances and accurately reconnect them with an appropriate target. Using microtools and nanotools we have developed a new method to rapidly initiate, elongate, and precisely connect new functional neuronal circuits over long distances. The extension rates achieved are ≥60 times faster than previously reported. Our findings have direct implications for the development of new therapies and surgical techniques to achieve functional regeneration after trauma and in neurodegenerative diseases. It also opens the door for the direct wiring of robust brain-machine interfaces as well as for investigations of fundamental aspects of neuronal signal processing and neuronal function.

Quantum state readout of individual quantum dots by electrostatic force detection.

Electric charge detection by atomic force microscopy (AFM) with single-electron resolution (e-EFM) is a promising way to investigate the electronic level structure of individual quantum dots (QDs). The oscillating AFM tip modulates the energy of the QDs, causing single electrons to tunnel between QDs and an electrode. The resulting oscillating electrostatic force changes the resonant frequency and damping of the AFM cantilever, enabling electrometry with a single-electron sensitivity. Quantitative electronic level spectroscopy is possible by sweeping the bias voltage. Charge stability diagram can be obtained by scanning the AFM tip around the QD. e-EFM technique enables to investigate individual colloidal nanoparticles and self-assembled QDs without nanoscale electrodes. e-EFM is a quantum electromechanical system where the back-action of a tunneling electron is detected by AFM; it can also be considered as a mechanical analog of admittance spectroscopy with a radio frequency resonator, which is emerging as a promising tool for quantum state readout for quantum computing. In combination with the topography imaging capability of the AFM, e-EFM is a powerful tool for investigating new nanoscale material systems which can be used as quantum bits.

Universal Aging Mechanism for Static and Sliding Friction of Metallic Nanoparticles.

The term "contact aging" refers to the temporal evolution of the interface between a slider and a substrate usually resulting in increasing friction with time. Current phenomenological models for multiasperity contacts anticipate that such aging is not only the driving force behind the transition from static to sliding friction, but at the same time influences the general dynamics of the sliding friction process. To correlate static and sliding friction on the nanoscale, we show experimental evidence of stick-slip friction for nanoparticles sliding on graphite over a wide dynamic range. We can assign defined periods of aging to the stick phases of the particles, which agree with simulations explicitly including contact aging. Additional slide-hold-slide experiments for the same system allow linking the sliding friction results to static friction measurements, where both friction mechanisms can be universally described by a common aging formalism.

Selective in situ potential-assisted SAM formation on multi electrode arrays.

The selective modification of individual components in a biosensor array is challenging. To address this challenge, we present a generalizable approach to selectively modify and characterize individual gold surfaces in an array, in an in situ manner. This is achieved by taking advantage of the potential dependent adsorption/desorption of surface-modified organic molecules. Control of the applied potential of the individual sensors in an array where each acts as a working electrode provides differential derivatization of the sensor surfaces. To demonstrate this concept, two different self-assembled monolayer (SAM)-forming electrochemically addressable ω-ferrocenyl alkanethiols (C11) are chemisorbed onto independent but spatially adjacent gold electrodes. The ferrocene alkanethiol does not chemisorb onto the surface when the applied potential is cathodic relative to the adsorption potential and the electrode remains underivatized. However, applying potentials that are modestly positive relative to the adsorption potential leads to extensive coverage within 10 min. The resulting SAM remains in a stable state while held at potentials <200 mV above the adsorption potential. In this state, the chemisorbed SAM does not significantly desorb nor do new ferrocenylalkythiols adsorb. Using three set applied potentials provides for controlled submonolayer alkylthiol marker coverage of each independent gold electrode. These three applied potentials are dependent upon the specifics of the respective adsorbate. Characterization of the ferrocene-modified electrodes via cyclic voltammetry demonstrates that each specific ferrocene marker is exclusively adsorbed to the desired target electrode.

Adsorption of PTCDA and C60 on KBr(001): electrostatic interaction versus electronic hybridization.

The adsorption of functional molecules on insulator surfaces is of great interest to molecular and organic electronics. Here, we present a systematic investigation of the geometric and electronic properties of perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA) and C60 on KBr(001) using density functional theory and non-contact atomic force microscopy to reveal the interplay of interactions between aromatic molecules and insulating substrates. Energetic and structural details are discussed, as well as electronic structures, e.g. local electronic density of states, (differential) charge density, and Bader charge analysis, were inspected. Electrostatics was found to be the primary interaction mechanism for systems of PTCDA and C60 adsorbed on KBr, which can be further promoted by electronic hybridizations of non-polar, but polarizable, molecules with substrates, e.g. C60/KBr(001). Electronic hybridization, depending on the polarizability of the π-system, may be suppressed by introducing high electron affinity atoms, e.g. O, into the molecule. Besides, we investigate molecules adsorbed on two-layer KBr(001) covered Cu(001), in which no hybridisation was found between PTCDA and the metal underneath, but a C-Br-Cu hybridized state in C60/KBr(001)/Cu(001). Since the interaction mechanism is dominated by electrostatics, it is concluded that alkali-halides are interesting and important materials for investigation, due to the minor influence on the molecular electronic structure, which may inspire new research fields of electronics.

Sensitivity measurement of a cantilever-based surface stress sensor.

A detailed analysis of the temporal surface stress evolution for potential-driven adsorption of ions is discussed. A gold-coated cantilever is used to simultaneously measure the change in surface stress as well as the current response during an applied potential step. In this electrochemical configuration, the cantilever acts as the working electrode, a platinum wire as the counter electrode, and the Ag/AgCl (sat. KCl) electrode as the reference electrode. To study the time-dependent signal and the sensitivity of the cantilever response, the frequency of the potential step applied to the cantilever is varied from 1 s to 0.1 ms. First, a comparison between a strong adsorbing (chloride Cl-) and a weak adsorbing ion (perchlorate ClO4-) in a 1 mM solution is presented. Next, the linear relationship between surface stress and charge density is measured for these fast potential steps. The slope of this fit is defined as the sensitivity of the system and is shown to increase for shorter potential pulses. Finally, the behaviour of the surface stress and current for consecutive applied potential steps is studied.

Revealing energy level structure of individual quantum dots by tunneling rate measured by single-electron sensitive electrostatic force spectroscopy.

We present theoretical and experimental studies of the effect of the density of states of a quantum dot (QD) on the rate of single-electron tunneling that can be directly measured by electrostatic force microscopy (e-EFM) experiments. In e-EFM, the motion of a biased atomic force microscope cantilever tip modulates the charge state of a QD in the Coulomb blockade regime. The charge dynamics of the dot, which is detected through its back-action on the capacitavely coupled cantilever, depends on the tunneling rate of the QD to a back-electrode. The density of states of the QD can therefore be measured through its effect on the energy dependence of tunneling rate. We present experimental data on individual 5 nm colloidal gold nanoparticles that exhibit a near continuous density of state at 77 K. In contrast, our analysis of already published data on self-assembled InAs QDs at 4 K clearly reveals discrete degenerate energy levels.

Conductivity of an atomically defined metallic interface.

A mechanically formed electrical nanocontact between gold and tungsten is a prototypical junction between metals with dissimilar electronic structure. Through atomically characterized nanoindentation experiments and first-principles quantum transport calculations, we find that the ballistic conduction across this intermetallic interface is drastically reduced because of the fundamental mismatch between s wave-like modes of electron conduction in the gold and d wave-like modes in the tungsten. The mechanical formation of the junction introduces defects and disorder, which act as an additional source of conduction losses and increase junction resistance by up to an order of magnitude. These findings apply to nanoelectronics and semiconductor device design. The technique that we use is very broadly applicable to molecular electronics, nanoscale contact mechanics, and scanning tunneling microscopy.