Table of contents

We investigate translocation of linear and circular double-stranded DNA molecules through solid state nanopores where each molecule is recaptured and re-translocated many times. Single molecules can be recaptured by switching voltage polarity for hundreds or even thousands of times. The large number of recapture events allows statistics on the translocation of individual molecules. Surprisingly, we observe that recaptured DNA molecules do not translocate in a linear head-to-tail fashion, but instead translocate as a folded blob where multiple parts of the DNA molecule simultaneously translocate through the pore in parallel. This folding is observed through the presence of up to 13 DNA double strands from the same molecule simultaneously inside the pore, as well as many smaller fold numbers occurring during the course of a translocation event. The strong folding is particularly prominent when the molecule is recaptured at short timescales, i.e. shorter than its characteristic time to relax to its equilibrium configuration. At longer recapture times, both the amount of folding and the mean duration of translocation approach the values observed in non-recapture experiments. The data shows that the translocation time of a molecule depends on the molecule's conformation at the start of the translocation process, with extended molecules having a longer translocation time. The observations can be attributed to a high-density non-equilibrium DNA configuration that arises in the close vicinity of the nanopore immediately after translocation, which dissipates on a timescale given by the Zimm relaxation time.

Typical photoluminescent semiconductor nanoparticles, called quantum dots (QDs), have potential applications in biological labeling. When used to label stem cells, QDs may impair the differentiation capacity of the stem cells. In this study, we synthesized zinc oxide (ZnO) QDs in methanol with an average size of ∼2 nm. We then employed two different types of polyethylene glycol (PEG) molecules (SH-PEG-NH₂ and NH₂-PEG-NH₂) to conjugate ZnO QDs and made them water-dispersible. Fourier transform infrared spectroscopy spectra indicated the attachment of PEG molecules on ZnO QDs. No obvious size alteration was observed for ZnO QDs after PEG conjugation. The water-dispersible ZnO QDs still retained the antibacterial activity and fluorescence intensity. The cytotoxicity evaluation revealed that ZnO QDs at higher concentrations decreased cell viability but were generally safe at 30 ppm or below. Cell lines of hepatocytes (HepG2), osteoblasts (MC3T3-E1) and mesenchymal stem cells (MSCs) were successfully labeled by the water-dispersible ZnO QDs at 30 ppm. The ZnO QD-labeled MSCs maintained their stemness and differentiation capacity. Therefore, we conclude that the water-dispersible ZnO QDs developed in this study have antibacterial activity, low cytotoxicity, and proper labeling efficiency, and can be used to label a variety of cells including stem cells.

Cancer cells can express specific biomarkers, such as cell membrane proteins and signaling factors. Thus, finding biomarkers and delivering diagnostic agents are important in the diagnosis of cancer. In this study, we investigated a biomarker imaging agent for the diagnosis of hepatic cancers. The asialoglycoprotein receptor (ASGPr) was selected as a biomarker for hepatoma cells and the ASGPr-targetable imaging agent bearing a galactosyl group was prepared using manganese ferrite nanoparticles (MFNP) and galactosylgluconic acid. The utility of the ASGPr-targetable imaging agent, galactosylated MFNP (G-MFNP) was assessed by several methods in ASGPr-expressing HepG2 cells as target cells and ASGPr-deficient MCF7 cells. Physical and chemical properties of G-MFNP were examined using Fourier-transform infrared spectroscopy, dynamic light scattering, zeta potential analysis, and transmission electron microscopy. No significant cytotoxicity was observed in either cell line. Targeting ability was assessed using flow cytometry, magnetic resonance imaging, inductively coupled plasma atomic emission spectroscopy, absorbance analysis, dark-field microscopy, Prussian blue staining, and transmission electron microscopy. We demonstrated that G-MFNP target successfully and bind to ASGPr-expressing HepG2 cells specifically. We suggest that these results will be useful in strategies for cancer diagnoses based on magnetic resonance imaging.

The electrical transport of the highly conductive poly-(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) is investigated with Ohmic and spin-polarized tunnel contacts at nanoscale lateral dimensions. Temperature-dependent charge transport measurements reveal that electrical conductivity scales non-linearly as a function of electrode spacing, which is attributed to the localization of carriers induced by the disorder introduced by the PSS polyelectrolyte. In addition, we demonstrate the integration of this conducting polymer in nanoscale lateral spin-valve devices by increasing the pH of the PEDOT:PSS solution. We present charge and magnetotransport measurement results of NiFe/AlO_x/PEDOT:PSS/AlO_x/NiFe lateral structures for various thicknesses of the alumina tunnel barriers. We discuss the absence of magnetoresistance of our spin valves within the framework of Valet–Fert theory, and estimate an upper limit for the spin lifetime of carriers in PEDOT:PSS to τ_sf ⩽ 50 ns.

We report the fabrication of a flexible graphene-based nonvolatile memory device using Pb(Zr_0.35,Ti_0.65)O₃ (PZT) as the ferroelectric material. The graphene and PZT ferroelectric layers were deposited using chemical vapor deposition and sol–gel methods, respectively. Such PZT films show a high remnant polarization (P_r) of 30 μC cm⁻² and a coercive voltage (V_c) of 3.5 V under a voltage loop over ±11 V. The graphene–PZT ferroelectric nonvolatile memory on a plastic substrate displayed an on/off current ratio of 6.7, a memory window of 6 V and reliable operation. In addition, the device showed one order of magnitude lower operation voltage range than organic-based ferroelectric nonvolatile memory after removing the anti-ferroelectric behavior incorporating an electrolyte solution. The devices showed robust operation in bent states of bending radii up to 9 mm and in cycling tests of 200 times. The devices exhibited remarkable mechanical properties and were readily integrated with plastic substrates for the production of flexible circuits.

This study presents the superior structural versatility of strained silicon nitride (SiN_x) membranes as a platform for three-dimensional (3D) hierarchical tubular architectures. The effects of compressive and tensile stressed SiN_x layer thickness on the self-rolled-up tube curvature, the sacrificial layer etching anisotropy on rolling direction and chirality, and stress engineering by localized thickness control or thermal treatment, are explored systematically. Using strained SiN_x membranes as an electrically insulating and optically transparent mechanical support, compact 3D hierarchical architectures involving carbon nanotube arrays and passive electronic components are demonstrated by releasing the functional structures deposited and patterned in 2D. These examples highlight the uniqueness of this platform that exploits 2D processing and self-assembly to achieve highly functional 3D structures.

Indium phosphide nanowires were grown by metalorganic molecular beam epitaxy using the selective-area vapor–liquid–solid method. We show experimentally and theoretically that the size of the annular opening around the nanowire has a major impact on nanowire growth rate. In addition, we observed a considerable reduction of the growth rate in dense two-dimensional arrays, in agreement with a calculation of the shadowing of the scattered precursors. Due to the impact of these effects on growth, they should be considered during selective-area vapor–liquid–solid nanowire epitaxy.

Nanowires made of materials with non-centrosymmetric crystal structures are expected to be ideal building blocks for self-powered nanodevices due to their piezoelectric properties, yet a controversial explanation of the effective operational mechanisms and size effects still delays their real exploitation. To solve this controversy, we propose a methodology based on DFT calculations of the response of nanostructures to external deformations that allows us to distinguish between the different (bulk and surface) contributions: we apply this scheme to evaluate the piezoelectric properties of ZnO [0001] nanowires, with a diameter up to 2.3 nm. Our results reveal that, while surface and confinement effects are negligible, effective strain energies, and thus the nanowire mechanical response, are dependent on size. Our unified approach allows for a proper definition of piezoelectric coefficients for nanostructures, and explains in a rigorous way the reason why nanowires are found to be more sensitive to mechanical deformation than the corresponding bulk material.

We report on a simple strategy for the direct synthesis of a thin film comprising interconnected NiO nanoparticles deposited on both sides of a graphene sheet via cathodic deposition. For the co-electrodeposition, graphene oxide (GO) is treated with water-soluble cationic poly(ethyleneimine) (PEI) which acts as a stabilizer and trapping agent to form complexes of GO and Ni²⁺. The positively charged complexes migrate toward the stainless steel substrate, resulting in the electrochemical deposition of PEI-modified GO/Ni(OH)₂ at the electrode surface under an applied electric field. The as-synthesized film is then converted to graphene/NiO after annealing at 350 ° C. The interconnected NiO nanoparticles are uniformly deposited on both sides of the graphene surface, as evidenced by field emission scanning electron microscopy, transmission electron microscopy and energy dispersive spectrometry. This graphene/NiO structure shows enhanced electrochemical performance with a large reversible capacity, good cyclic performance and improved electronic conductivity as an anode material for lithium ion batteries. A reversible capacity is retained above 586 mA h g⁻¹ after 50 cycles. The findings reported herein suggest that this strategy can be effectively used to overcome a bottleneck problem associated with the electrochemical production of graphene/metal oxide films for lithium ion battery anodes.

A new touch sensor device has been demonstrated with molybdenum disulfide (MoS₂) field effect transistors stacked with a piezoelectric polymer, polyvinylidene fluoride–trifluoroethylene (PVDF–TrFE). The performance of two device stack structures, metal/PVDF–TrFE/MoS₂ (MPM) and metal/PVDF–TrFE/Al₂O₃/MoS₂ (MPAM), were compared as a function of the thickness of PVDF–TrFE and Al₂O₃. The sensitivity of the touch sensor has been improved by two orders of magnitude by reducing the charge scattering and enhancing the passivation effects using a thin Al₂O₃ interfacial layer. Reliable switching behavior has been demonstrated up to 120 touch press cycles.

A rice-straw-like silicon nanowire (SiNW) array was developed for hydrogen gas sensing applications. The straight-aligned SiNW array sensor was first fabricated by the metal-assisted electroless etching (MAEE) technique. Rice-straw-like SiNW arrays were formed using a repeated MAEE technique. Hydrogen sensing characteristics were measured for gas concentrations from 20 to 1000 ppm at room temperature. The rice-straw-like SiNW-array-based hydrogen gas sensor performed with low noise and a high response (232.5%) for 1000 ppm hydrogen gas. It was found that the rice-straw-like SiNW-array hydrogen gas sensor had a much better response (approximately 2.5 times) than the straight-aligned SiNW-array sensor. The rice-straw-like SiNW-array structure effectively increased the surface area and the concentration of silicon oxide, which provided additional binding sites for gas molecules. Thus, the rice-straw-like SiNW-array-based hydrogen gas sensor possessed good sensing properties and has the potential for mass production of sensing devices.

Impressive opto-electronic devices and transistors have recently been fabricated from GaAs nanopillars grown by catalyst-free selective-area epitaxy, but this growth technique has always resulted in high densities of stacking faults. A stacking fault occurs when atoms on the growing (111) surface occupy the sites of a hexagonal-close-pack (hcp) lattice instead of the normal face-centered-cubic (fcc) lattice sites. When stacking faults occur consecutively, the crystal structure is locally wurtzite instead of zinc-blende, and the resulting band offsets are known to negatively impact device performance. Here we present experimental and theoretical evidence that indicate stacking fault formation is related to the size of the critical nucleus, which is temperature dependent. The difference in energy between the hcp and fcc orientation of small nuclei is computed using density-function theory. The minimum energy difference of 0.22 eV is calculated for a nucleus with 21 atoms, so the population of nuclei in the hcp orientation is expected to decrease as the nucleus grows larger. The experiment shows that stacking fault occurrence is dramatically reduced from 22% to 3% by raising the growth temperature from 730 to 790 ° C. These data are interpreted using classical nucleation theory which dictates a larger critical nucleus at higher growth temperature.

Highly-qualified graphene was prepared by the ultrasonic exfoliation of commercial expanded graphite (EG) under the promotion of (NH₄)₂CO₃ decomposition. The yield of graphene from the first exfoliation is 7 wt%, and it can be increased to more than 65 wt% by repeated exfoliations. Atomic force microscopy, x-ray photoelectron spectroscopy and Raman analysis show that the as-prepared graphene only has a few defects or oxides, and more than 95% of the graphene flakes have a thickness of ∼1 nm. The electrochemical performance of the as-prepared graphene is comparable to reduced graphene oxide in the determination of dopamine (DA) from the mixed solution of ascorbic acid, uric acid and DA. These results show that the decomposition of (NH₄)₂CO₃ molecules in the EG layers under ultrasonication promotes the exfoliation of graphite and provides a low-priced route for large scale production of highly-quality graphene.

In this paper, we present an innovative method for the synthesis of CdTe/CdSe type-II core/shell structure quantum dots (QDs) using 'greener' chemicals. The PL of CdTe/CdSe type-II core/shell structure QDs ranges from 600 to 820 nm, and the as-synthesized core/shell structures show narrow size distributions and stable and high quantum yields (50–75%). Highly efficient near-infrared light-emitting diodes (LEDs) have been demonstrated by employing the CdTe/CdSe type-II core/shell QDs as emitters. The devices fabricated based on these type-II core/shell QDs show color-saturated near-infrared emission from the QD layers, a low turn-on voltage of 1.55 V, an external quantum efficiency (EQE) of 1.59%, and a current density and maximum radiant emittance of 2.1 × 10³ mA cm⁻² and 17.7 mW cm⁻² at 8 V; it is the first report to use type-II core/shell QDs as near-infrared emitters and these results may offer a practicable platform for the realization of near-infrared QD-based light-emitting diodes, night-vision-readable displays, and friend/foe identification system.

Atomic force microscopy (AFM), conductive AFM and electrochemical strain microscopy were used to study the topography change at the defect surface of SrTiO₃:N, breakdown in the electrical conduction of the tip/sample/electrode system and ionic motion. The IV curves show resistance switching behavior in a voltage range ±6 V < U <± 10 V and a current of maximum ±10 nA. A series of sweeping IV curves resulted in an increase in ionically polarized states (surface charging), electrochemical volume (surface deformations) and sequential formations of stable surface protrusions. The surface deformations are reversible (U <± 5 V) without IV pinched hysteresis and remained stable during the resistance switching (U >± 6 V), revealing the additional necessity (albeit insufficient due to 50% yield of working cells) of surface protrusion formation for resistance switching memory.

Conventional Kelvin probe force microscopy (KPFM) relies on closed loop (CL) bias feedback for the determination of surface potential (SP). However, SP measured by CL-KPFM has been shown to be strongly influenced by the choice of measurement parameters due to non-electrostatic contributions to the input signal of the bias feedback loop. This often leads to systematic errors of several hundred mV and can also result in topographical crosstalk. Here, open loop (OL)-KPFM modes are investigated as a means of obtaining a quantitative, crosstalk free measurement of the SP of graphene grown on Cu foil, and are directly contrasted with CL-KPFM. OL-KPFM operation is demonstrated in both single and multi-frequency excitation regimes, yielding quantitative SP measurements. The SP difference between single and multilayer graphene structures using OL-KPFM was found to be 63 ± 11 mV, consistent with values previously reported by CL-KPFM. Furthermore, the same relative potential difference between Al₂O₃-coated graphene and Al₂O₃-coated Cu was observed using both CL and OL techniques. We observed an offset of 55 mV between absolute SP values obtained by OL and CL techniques, which is attributed to the influence of non-electrostatic contributions to the input of the bias feedback used in CL-KPFM.

A comparative study on the structural and magnetic properties of highly ordered hexagonal arrays of Co nanoholes, nanowires, nanopillars and nanotubes, with tuned pore/wire/tube diameters, is here presented. The magnetic interactions and their dependence on the geometric features of the arrays were studied using first-order reversal curves (FORCs). For all nanostructures we observe an increase of the magnetostatic interactions with the templates' pore diameter, with the higher (smaller) values found for the nanowire (nanohole) arrays. For the smallest diameters studied (35 nm), all types of arrays could be considered as almost isolated nanostructures, where local interactions prevail. In particular, both nanotube and nanohole arrays exhibit considerable local magnetostatic interactions coming from the stray fields within each void or empty core. On the other hand, the coercivity is found to decrease with diameter for the elongated nanostructures, while it increases with the pore diameter for the nanohole arrays. This behavior is associated with the magnetization reversal mechanisms present in each array. This work highlights a versatile route to tailor the size, geometrical arrangement and magnetostatic interactions of ordered arrays and demonstrates their importance for the tuning of the magnetic behavior of nanometric devices.

We report on transient adhesion and conductance phenomena associated with tip wetting in mechanical contacts produced by the indentation of a clean W(111) tip into a Au(111) surface. A combination of atomic force microscopy and scanning tunneling microscopy was used to carry out indentation and to image residual impressions in ultra-high vacuum. The ∼7 nm radii tips used in these experiments were prepared and characterized by field ion microscopy in the same instrument. The very first indentations of the tungsten tips show larger conductance and pull-off adhesive forces than subsequent indentations. After ∼30 indentations to a depth of ∼1.7 nm, the maximum conductance and adhesion forces reach steady state values approximately 12 ×  and 6 ×  smaller than their initial value. Indentation of W(111) tips into Cu(100) was also performed to investigate the universality of tip wetting phenomena with a different substrate. We propose a model from contact mechanics considerations which quantitatively reproduces the observed decay rate of the conductance and adhesion drops with a 1/e decay constant of 9–14 indentation cycles. The results show that the surface composition of an indenting tip plays an important role in defining the mechanical and electrical properties of indentation contacts.

We demonstrate that core/graded-shell CdSe/CdSe_1−xS_x/CdS giant semiconductor nanocrystals (g-NCs) have robust photoluminescence (PL) temperature response. At a size of 10.2 nm in diameter, these g-NCs undergo a PL drop of only 30% at 355 K relative to their PL intensity at 85 K. In comparison, the core/step-shell CdSe/CdS g-NCs at the same diameter exhibit 80% PL drop at 355 K. Spectral shifting and broadening were found to be, respectively, 5–10 times and 2–4 times smaller than those observed in standard CdSe core and CdSe/CdS core/shell NCs. These core/graded-shell g-NCs are largely blinking suppressed and have insignificant photoluminescence decay even after excitation at very high irradiance (44 kW cm⁻²) for over an hour. These types of g-NC have potential applications as the active medium for thermally robust laser devices (in the visible range) or as temperature-insensitive bioprobes for biomedical imaging.

Bimodal atomic force microscopy (AFM) is a recently developed technique of dynamic AFM where a higher eigenmode of the cantilever is simultaneously excited along with the fundamental eigenmode. The effects of different operating parameters while imaging an impact copolymer blend of polypropylene (PP) and ethylene–propylene (E–P) rubber in bimodal mode are explored through experiments and numerical simulations. The higher mode amplitude and phase contrasts between the two components of the sample reverse at different points as the free amplitude of the higher eigenmode is increased. Three different regimes are identified experimentally depending on the relative contrast between the PP and the E–P rubber. It is observed that the kinetic energy and free air drive input energy of the two cantilever eigenmodes play a role in determining the regimes of operation. Numerical simulations conducted with appropriate tip–sample interaction forces support the experimental results. An understanding of these regimes and the associated cantilever dynamics will guide a rational approach towards selecting appropriate operating parameters.

The deformation mechanism and mechanical properties of carbon nanotube (CNT) forests conformally coated with alumina using atomic layer deposition (ALD) are investigated using in situ and ex situ micro-indentation. While micro-indentation of a CNT forest coated with a thin discontinuous layer using 20 ALD cycles results in a deformation response similar to the response of uncoated CNT forests, a similar test on a CNT forest coated with a sufficiently thick and continuous layer using 100 ALD cycles causes fracture of both the alumina coatings and the core CNTs. With a 10 nm coating, 4-fold and 14-fold stiffness increases are measured using a flat punch and a Berkovich tip, respectively. Indentation testing with the Berkovich tip also reveals increased recoverability at relatively low strains. The results show that ALD coated CNT forests could be useful for applications that require higher stiffness or recoverability. Also, fracturing of the nanotubes shows that upper limits exist in the loading of conformally coated CNT forests.

Epitaxial growth of electrodes and tunnel barriers on graphene is one of the main technological bottlenecks for graphene spintronics. In this paper, we demonstrate that MgO(111) epitaxial tunnel barriers, one of the prime candidates for spintronic application, can be grown by molecular beam epitaxy on epitaxial graphene on SiC(0001). Ferromagnetic metals (Fe, Co, Fe₂₀Ni₈₀) were epitaxially grown on top of the MgO barrier, thus leading to monocrystalline electrodes on graphene. Structural and magnetic characterizations were performed on these ferromagnetic metals after annealing and dewetting: they form clusters with a 100 nm typical lateral width, which are mostly magnetic monodomains in the case of Fe. This epitaxial stack opens the way to graphene spintronic devices taking benefits from a coherent tunnelling current through the epitaxial MgO/graphene stack.