Tuning the Liquid-Vapour Interface of VLS Epitaxy for Creating Novel Semiconductor Nanostructures.

Controlling the morphology and composition of semiconductor nano- and micro-structures is crucial for fundamental studies and applications. Here, Si-Ge semiconductor nanostructures were fabricated using photolithographically defined micro-crucibles on Si substrates. Interestingly, the nanostructure morphology and composition of these structures are strongly dependent on the size of the liquid-vapour interface (i.e., the opening of the micro-crucible) in the CVD deposition step of Ge. In particular, Ge crystallites nucleate in micro-crucibles with larger opening sizes (3.74-4.73 µm2), while no such crystallites are found in micro-crucibles with smaller openings of 1.15 µm2. This interface area tuning also results in the formation of unique semiconductor nanostructures: lateral nano-trees (for smaller openings) and nano-rods (for larger openings). Further TEM imaging reveals that these nanostructures have an epitaxial relationship with the underlying Si substrate. This geometrical dependence on the micro-scale vapour-liquid-solid (VLS) nucleation and growth is explained within a dedicated model, where the incubation time for the VLS Ge nucleation is inversely proportional to the opening size. The geometric effect on the VLS nucleation can be used for the fine tuning of the morphology and composition of different lateral nano- and micro-structures by simply changing the area of the liquid-vapour interface.

Dendritic Polyglycerol Amine: An Enhanced Substrate to Support Long-Term Neural Cell Culture.

Long-term stable cell culture is a critical tool to better understand cell function. Most adherent cell culture models require a polymer substrate coating of poly-lysine or poly-ornithine for the cells to adhere and survive. However, polypeptide-based substrates are degraded by proteolysis and it remains a challenge to maintain healthy cell cultures for extended periods of time. Here, we report the development of an enhanced cell culture substrate based on a coating of dendritic polyglycerol amine (dPGA), a non-protein macromolecular biomimetic of poly-lysine, to promote the adhesion and survival of neurons in cell culture. We show that this new polymer coating provides enhanced survival, differentiation and long-term stability for cultures of primary neurons or neurons derived from human induced pluripotent stem cells (hiPSCs). Atomic force microscopy analysis provides evidence that greater nanoscale roughness contributes to the enhanced capacity of dPGA-coated surfaces to support cells in culture. We conclude that dPGA is a cytocompatible, functionally superior, easy to use, low cost and highly stable alternative to poly-cationic polymer cell culture substrate coatings such as poly-lysine and poly-ornithine. Summary statementHere, we describe a novel dendritic polyglycerol amine-based substrate coating, demonstrating superior performance compared to current polymer coatings for long-term culture of primary neurons and neurons derived from induced pluripotent stem cells.

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.

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.

Charge Carrier Inversion in a Doped Thin Film Organic Semiconductor Island.

Inducing an inversion layer in organic semiconductors is a highly nontrivial, but critical, achievement for producing organic field-effect transistor (OFET) devices, which rely on the generation of inversion, accumulation, and depletion regimes for successful operation. Here, we develop a pulsed bias technique to characterize the dopant type of any organic material system, without prior knowledge or characterization of the material in question. We use this technique on a pentacene/PTCDI heterostructure and thus deduce that pentacene is exhibiting n-doped like response. The source of the additional charges in the pentacene island can be identified by charging rings in the dissipation channel of the noncontact atomic force microscopy (AFM) signal, a typical signature for localized charge transfer from the AFM tip to the sample. Additionally, through tip-induced band-bending, we generate inversion, depletion, and accumulation regimes over a 20 nm radius, three monolayer thick n-doped pentacene island. Our findings demonstrate that nanometer-scale lateral extent and thickness are sufficient for an OFET device to operate in the inversion regime.

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.

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.

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.

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.

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.

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.

Response of mechanically-created neurites to extension.

We use micromanipulation techniques and real-time particle tracking to develop an approach to study specific attributes of neuron mechanics. We use a mechanical probe composed of a hollow micropipette with its tip fixed to a functionalized bead to induce the formation of a neurite in a sample of rat hippocampal neurons. We then move the sample relative to the pipette tip, elongating the neurite while simultaneously measuring its tension by optically tracking the deflection of the beaded tip. By calibrating the spring constant of the pipette, we can convert this deflection to a force. We use this technique to obtain uniaxial strain measurements of induced neurites and investigate the dependence of the force-extension relationship on mechanical pull speed. We show that in the range of pull speeds studied (0.05-1.8 µm/s), the variation in the work to extend a neurite 10 µm is consistent across pull speeds. We do not observe statistically significant rate-dependent effects in the force-extension profiles; instead we find the same quadratic behaviour (with parameters drawn from the same distributions) at each pull speed.

Review of time-resolved non-contact electrostatic force microscopy techniques with applications to ionic transport measurements.

Recently, there have been a number of variations of electrostatic force microscopy (EFM) that allow for the measurement of time-varying forces arising from phenomena such as ion transport in battery materials or charge separation in photovoltaic systems. These forces reveal information about dynamic processes happening over nanometer length scales due to the nanometer-sized probe tips used in atomic force microscopy. Here, we review in detail several time-resolved EFM techniques based on non-contact atomic force microscopy, elaborating on their specific limitations and challenges. We also introduce a new experimental technique that can resolve time-varying signals well below the oscillation period of the cantilever and compare and contrast it with those previously established.

Calibration of the oscillation amplitude of electrically excited scanning probe microscopy sensors.

Atomic force microscopy (AFM) is an analytical surface characterization tool which can reveal a sample's topography with high spatial resolution while simultaneously probing tip-sample interactions. Local measurement of chemical properties with high-resolution has gained much popularity in recent years with advances in dynamic AFM methodologies. A calibration factor is required to convert the electrical readout to a mechanical oscillation amplitude in order to extract quantitative information about the surface. We propose a new calibration technique for the oscillation amplitude of electrically driven probes using the principle of energy balance. Our technique relies on the measurement of the energy input to maintain the oscillation amplitude constant. With the measurement of the energy input to the probe, a mechanical oscillation amplitude is calculated and a calibration factor to convert the electrical readout in volts to a mechanical oscillation amplitude in Ångströms is obtained. We demonstrate the application of the new technique with a quartz tuning fork including the qPlus configuration, while the same principle can be applied to other piezoelectric resonators such as length extension resonators or piezoelectric cantilevers. The calibration factor obtained by this technique is found to be in agreement with using the thermal noise spectrum method for capsulated and decapsulated tuning forks and tuning forks in the qPlus configuration.

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.

Dendritic Polyglycerol Sulfates in the Prevention of Synaptic Loss and Mechanism of Action on Glia.

Dendritic polyglycerols (dPG), particularly dendritic polyglycerol sulfates (dPGS), have been intensively studied due to their intrinsic anti-inflammatory activity. As related to brain pathologies involving neuroinflammation, the current study examined if dPG and dPGS can (i) regulate neuroglial activation, and (ii) normalize the morphology and function of excitatory postsynaptic dendritic spines adversely affected by the neurotoxic 42 amino acid amyloid-ß (Aß42) peptide of Alzheimer disease (AD). The exact role of neuroglia, such as microglia and astrocytes, remains controversial especially their positive and negative impact on inflammatory processes in AD. To test dPGS effectiveness in AD models we used primary neuroglia and organotypic hippocampal slice cultures exposed to Aß42 peptide. Overall, our data indicate that dPGS is taken up by both microglia and astrocytes in a concentration- and time-dependent manner. The mechanism of action of dPGS involves binding to Aß42, i.e., a direct interaction between dPGS and Aß42 species interfered with Aß fibril formation and reduced the production of the neuroinflammagen lipocalin-2 (LCN2) mainly in astrocytes. Moreover, dPGS normalized the impairment of neuroglia and prevented the loss of dendritic spines at excitatory synapses in the hippocampus. In summary, dPGS has desirable therapeutic properties that may help reduce amyloid-induced neuroinflammation and neurotoxicity in AD.

Rewiring Neuronal Circuits: A New Method for Fast Neurite Extension and Functional Neuronal Connection.

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. Here a procedure is described to rapidly initiate, elongate, and precisely connect new functional neuronal circuits over long distances. The extension rates achieved reach over 1.2 mm/h, 30-60 times faster than the in vivo rates of the fastest growing axons from the peripheral nervous system (0.02 to 0.04 mm/h)28 and 10 times faster than previously reported for the same neuronal type at an earlier stage of development4. First, isolated populations of rat hippocampal neurons are grown for 2-3 weeks in microfluidic devices to precisely position the cells, enabling easy micromanipulation and experimental reproducibility. Next, beads coated with poly-D-lysine (PDL) are placed on neurites to form adhesive contacts and pipette micromanipulation is used to move the resulting bead-neurite complex. As the bead is moved, it pulls out a new neurite that can be extended over hundreds of micrometers and functionally connected to a target cell in less than 1 h. This process enables experimental reproducibility and ease of manipulation while bypassing slower chemical strategies to induce neurite growth. Preliminary measurements presented here demonstrate a neuronal growth rate far exceeding physiological ones. Combining these innovations allows for the precise establishment of neuronal networks in culture with an unprecedented degree of control. It is a novel method that opens the door to a plethora of information and insights into signal transmission and communication within the neuronal network as well as being a playground in which to explore the limits of neuronal growth. The potential applications and experiments are widespread with direct implications for therapies that aim to reconnect neuronal circuits after trauma or in neurodegenerative diseases.

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.

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.