Variations in the Effective Work Function of Graphene in a Sliding Electrical Contact Interface under Ambient Conditions.

Control of work function (WF) in graphene is crucial for graphene application in electrode material replacement and electrode surface protection in optoelectronic devices. Although efforts have been made to manipulate the effective WF of graphene to optimize its application, most studies have focused on graphene employed in static electrical contact interfaces. In this work, we investigated WF variations of supported single-layer graphene (SLG) in sliding electrical contact under ambient conditions, which was achieved by sliding an electrically biased conductive atomic force microscopy (cAFM) probe on the SLG surface. The effective WF, structural properties, and chemical compositions of rubbed SLG were subsequently measured by Kelvin probe force microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy, respectively. We found that the effective WF of the rubbed SLG was governed by both the tunneling triboelectric effect (TTE) and tribochemical-induced surface functionalization. The TTE charges generated by the sliding cAFM probe tunneled through the structural defects of the SLG and were trapped underneath the SLG. The SLG will be either p-doped or n-doped depending on the type of TTE charges and the polarity of electric bias applied to the cAFM probe during the rubbing process. However, the applied electric bias also led to the electrolysis of a water meniscus formed at the cAFM probe-SLG contact, resulting in surface oxidation and the increase of SLG WF. Further absorption of ambient water molecules on the oxygenated functional groups gradually reduced the SLG WF. The influence of TTE and surface functionalization on the SLG WF depends on the magnitude and polarity of applied electric biases, relative humidity, and physical properties of the supporting substrates. Our results demonstrate that the effective WF of SLG in a sliding electrical contact interface will vary with time and might need to be considered for related applications.

Correlation between Nanoscale Elasticity, Semiconductivity, and Structural Order in Functionalized Polyaniline Thin Films.

The correlation between structural order, elasticity, and semiconductivity for butylthio-functionalized polyaniline (PANI-SBu) thin films was investigated using atomic force microscopy (AFM)-based techniques with X-ray diffraction (XRD) and scanning electron microscopy (SEM). After different stirring times, the thin films were cast from the solution of PANI-SBu in N-methyl-2-pyrrolidone that was continuously stirred at a constant rate of 150 rpm in an airtight round-bottom flask. According to the XRD and SEM results, the cross-sectional film structure evolved from being generally holey to highly lamellar with an increase in the stirring time. However, some new types of disordered structures began emerging beyond the optimal stirring time, possibly caused by the formation of disordered packing structures as contributed from the overoxidized polyaniline backbones during the additional stirring time. Moreover, according to the investigation results obtained using AFM-based techniques, the out-of-plane elastic moduli and charge mobilities of the PANI-SBu films were consistently smaller for disordered thin films and larger for structurally more ordered ones. The shear force resulting from the mechanical stirring of the PANI-SBu solution may gradually disentangle the polymer chains and thus help transform the individual polyaniline molecule from a coil-like chain conformation to a better extended rodlike chain conformation. Therefore, when cast into a film, the stretched polymer chains facilitate self-organization among the PANI-SBu backbones during the film formation process. Thus, an improved structural order in the film is attained. Our results demonstrate an unambiguous correlation between the structure order, elasticity, and conductivity in PANI-SBu thin films, which may have useful applications in conducting polymer-based flexible electronics.

Disease antigens detection by silicon nanowires with the efficiency optimization of their antibodies on a chip.

Enhancing the efficiency of antibody protein immobilized on a silicon nanowire-based chip for their antigens detection is reported. An external electric field (EEF) is applied to direct the orientation of antibodies during their immobilization on a chip. Atomic force microscopy (AFM) is used to measure the binding forces between immobilized antibody and targeting antigen under the influence of EEF at different angles. The maximum binding force under a specific angle (optimal angle; oa) of EEF (maxEEFoa) implies the optimal orientation of the antibodies on the chip. In this report, two different cancer carcinoembryonic antigen (CEA)-related cell adhesion molecules 5 (CEACAM5) & 1 (CEACAM1) were used for the examples of disease antigen detection. maxEEFoa of anti-CEACAM5 or anti-CEACAM1 immobilized on a general chip was firstly determined. Spectroscopy of AFM revealed that both binding forces were the largest ones with their antigens when maxEEFoa was applied as compared with no or other angles of EEF. These antibody proteins accompanied with the application of EEF were secondly immobilized on silicon-nanowires (n = 1000) and the field effects were measured (∆I) as their target antigens were approached. Results showed that ∆I was the largest ones when maxEEFoas (225°/270° and 135°/180° for anti-CEACAM5 and anti-CEACAM1, respectively) were applied as compared with other angles of EEF. These observations imply that the silicon nanowires together with the application of maxEEFoa as detection tools could be applied for the cancer diagnostics in the future.

Variations of the elastic modulus perpendicular to the surface of rubrene bilayer films.

Investigations exploring the inherent mechanical properties of electronic materials have grown rapidly in recent years largely because they are important in developing flexible electronics, organic displays and sensors. However, our understanding of the mechanical properties of organic semiconductors with a thin-film form remains limited. We report herein on an investigation of the structures and related elastic moduli perpendicular to the surface of a rubrene thin film. A rubrene/Si(100) film typically has a cluster-type morphology mainly comprising crystalline nanodomains within the film. We propose a structural bilayer model that can be used to explain the layered nature or characteristics of the rubrene films. As the film thickness is increased, the enhancement in elastic modulus can be attributed to the presence of a soft surface layer on a hard underlayer. Based on four-point probe measurements, the bilayered nature of such materials can be used to characterize their electrical resistive behavior while interfacial roughness is sensitive to the transport paths of conduction electrons. This information is valuable for future applications of organic semiconductors in flexible devices.

Frictional characteristics of nano-confined water mediated hole-doped single-layer graphene on silica surface.

We have investigated the frictional properties of single-layer graphene (SLG) coated rough silica substrate under the influence of nano-confined hydration layer underneath SLG. Through the friction and surface potential measurements by atomic force microscopy (AFM), we found polygonal features in AFM images of SLG-protected silica surface that exhibit simultaneously larger friction and higher surface potential as compared to their surrounding areas due to water layers confined under SLG. Nano-confined water layers at the SLG-silica interface can induce the hole-doping effect in SLG, resulting in a more positively-charged and hydrophilic surface that favors adsorption of ambient water molecules. Therefore, during friction measurements, nanoscale capillary bridges can form within the interstices of AFM probe-SLG contact, leading to larger adhesion and friction. The friction forces were found to respectively have negative and positive dependence on the sliding velocity inside and outside the polygonal regions due to different surface wettability. Hence, it is possible to manipulate the frictional properties of SLG-coated silica by the amount of hydration layer confined underneath SLG. Our results may find applications in friction control for future nano-devices.

High-Performance InSe Transistors with Ohmic Contact Enabled by Nonrectifying Barrier-Type Indium Electrodes.

The electrical contact to two-dimensional (2D) semiconductor materials is decisive to the electronic performance of 2D semiconductor field-effect devices (FEDs). The presence of a Schottky barrier often leads to a large contact resistance, which seriously limits the channel conductance and carrier mobility measured in a two-terminal geometry. In contrast, Ohmic contact is desirable and can be achieved by the presence of a nonrectifying or tunneling barrier. Here, we demonstrate that a nonrectifying barrier can be realized by contacting indium (In), a low work function metal, with layered InSe because of a favorable band alignment at the In-InSe interface. The nonrectifying barrier is manifested by Ohmic contact behavior at T = 2 K and a low barrier height, ΦB = 50 meV. This Ohmic contact enables demonstration of an on-current as large as 410 µA/µm, which is among the highest values achieved in FEDs based on layered semiconductors. A high electron mobility of 3700 and 1000 cm2/V·s is achieved with the two-terminal In-InSe FEDs at T = 2 K and room temperature, respectively, which can be attributed to enhanced quality of both conduction channel and the contacts. The improvement in the contact quality is further proven by an X-ray photoelectron spectroscopy study, which suggests that a reduction effect occurs at the In-InSe interface. The demonstration of high-performance In-InSe FEDs indicates a viable interface engineering method for next-generation, 2D semiconductor-based electronics.

Influence of Oxygen Vacancies on the Frictional Properties of Nanocrystalline Zinc Oxide Thin Films in Ambient Conditions.

Oxygen vacancy is the most studied point defect and has been found to significantly influence the physical properties of zinc oxide (ZnO). By using atomic force microscopy (AFM), we show that the frictional properties on the ZnO surface at the nanoscale greatly depend on the amount of oxygen vacancies present in the surface layer and the ambient humidity. The photocatalytic effect (PCE) is used to qualitatively control the amount of oxygen vacancies in the surface layer of ZnO and reversibly switch the surface wettability between hydrophobic and superhydrophilic states. Because oxygen vacancies in the ZnO surface can attract ambient water molecules, during the AFM friction measurement, water meniscus can form between the asperities at the AFM tip-ZnO contact due to the capillary condensation, leading to negative dependence of friction on the logarithm of tip sliding velocity. Such dependence is found to be a strong function of relative humidity and can be reversibly manipulated by the PCE. Our results indicate that it is possible to control the frictional properties of ZnO surface at the nanoscale using optical approaches.

Elastic coupling between layers in two-dimensional materials.

Two-dimensional materials, such as graphene and MoS2, are films of a few atomic layers in thickness with strong in-plane bonds and weak interactions between the layers. The in-plane elasticity has been widely studied in bending experiments where a suspended film is deformed substantially; however, little is known about the films' elastic modulus perpendicular to the planes, as the measurement of the out-of-plane elasticity of supported 2D films requires indentation depths smaller than the films' interlayer distance. Here, we report on sub-ångström-resolution indentation measurements of the perpendicular-to-the-plane elasticity of 2D materials. Our indentation data, combined with semi-analytical models and density functional theory, are then used to study the perpendicular elasticity of few-layer-thick graphene and graphene oxide films. We find that the perpendicular Young's modulus of graphene oxide films reaches a maximum when one complete water layer is intercalated between the graphitic planes. This non-destructive methodology can map interlayer coupling and intercalation in 2D films.

Measuring the elasticity of ribonucleotide(s)-containing DNA molecules using AFM.

Ribonucleotides, ribonucleoside monophosphates (rNMPs), have been revealed as possibly the most noncanonical nucleotides in genomic DNA. rNMPs, either not removed from Okazaki fragments during DNA replication or incorporated and scattered throughout the genome, pose a perturbation to the structure and a threat to the stability of DNA. The instability of DNA is mainly due to the extra 2'-hydroxyl (OH) group of rNMPs which give rise to local structural effects, which may disturb various molecular interactions in cells. As a result of these structural perturbations by rNMPs, the elastic properties of DNA are also affected. Here, we show the approach to test whether the presence of rNMPs in DNA duplexes could alter the elasticity of DNA by implementing atomic force microscopy (AFM)-based single molecule force-measurements of short rNMP(s)-containing oligonucleotides (oligos).

RNA intrusions change DNA elastic properties and structure.

The units of RNA, termed ribonucleoside monophosphates (rNMPs), have been recently found as the most abundant defects present in DNA. Despite the relevance, it is largely unknown if and how rNMPs embedded in DNA can change the DNA structure and mechanical properties. Here, we report that rNMPs incorporated in DNA can change the elastic properties of DNA. Atomic force microscopy (AFM)-based single molecule elasticity measurements show that rNMP intrusions in short DNA duplexes can decrease--by 32%--or slightly increase the stretch modulus of DNA molecules for two sequences reported in this study. Molecular dynamics simulations and nuclear magnetic resonance spectroscopy identify a series of significant local structural alterations of DNA containing embedded rNMPs, especially at the rNMPs and nucleotide 3' to the rNMP sites. The demonstrated ability of rNMPs to locally alter DNA mechanical properties and structure may help in understanding how such intrusions impact DNA biological functions and find applications in structural DNA and RNA nanotechnology.

Nanorheology by atomic force microscopy.

We present an Atomic Force Microscopy (AFM) based method to investigate the rheological properties of liquids confined within a nanosize gap formed by an AFM tip apex and a solid substrate. In this method, a conventional AFM cantilever is sheared parallel to a substrate surface by means of a lock-in amplifier while it is approaching and retracting from the substrate in liquid. The normal solvation forces and lateral viscoelastic shear forces experienced by the AFM tip in liquid can be simultaneously measured as a function of the tip-substrate distance with sub-nanometer vertical resolution. A new calibration method is applied to compensate for the linear drift of the piezo transducer and substrate system, leading to a more precise determination of the tip-substrate distance. By monitoring the phase lag between the driving signal and the cantilever response in liquid, the frequency dependent viscoelastic properties of the confined liquid can also be derived. Finally, we discuss the results obtained with this technique from different liquid-solid interfaces. Namely, octamethylcyclotetrasiloxane and water on mica and highly oriented pyrolytic graphite.

The interplay between apparent viscosity and wettability in nanoconfined water.

Understanding and manipulating fluids at the nanoscale is a matter of growing scientific and technological interest. Here we show that the viscous shear forces in nanoconfined water can be orders of magnitudes larger than in bulk water if the confining surfaces are hydrophilic, whereas they greatly decrease when the surfaces are increasingly hydrophobic. This decrease of viscous forces is quantitatively explained with a simple model that includes the slip velocity at the water surface interface. The same effect is observed in the energy dissipated by a tip vibrating in water perpendicularly to a surface. Comparison of the experimental data with the model shows that interfacial viscous forces and compressive dissipation in nanoconfined water can decrease up to two orders of magnitude due to slippage. These results offer a new understanding of interfacial fluids, which can be used to control flow at the nanoscale.

Adhesion and size dependent friction anisotropy in boron nitride nanotubes.

The frictional properties of individual multiwalled boron nitride nanotubes (BN-NTs) synthesized by chemical vapour deposition (CVD) and deposited on a silicon substrate are investigated using an atomic force microscope tip sliding along (longitudinal sliding) and across (transverse sliding) the tube's principal axis. Because of the tube's transverse deformations during the tip sliding, a larger friction coefficient is found for the transverse sliding as compared to the longitudinal sliding. Here, we show that the friction anisotropy in BN-NTs, defined as the ratio between transverse and longitudinal friction forces per unit area, increases with the nanotube-substrate contact area, estimated to be proportional to (L(NT)R(NT))(1/2), where L(NT) and R(NT) are the length and the radius of the nanotube, respectively. Larger contact area denotes stronger surface adhesion, resulting in a longitudinal friction coefficient closer to the value expected in the absence of transverse deformations. Compared to carbon nanotubes (C-NTs), BN-NTs display a friction coefficient in each sliding direction with intermediate values between CVD and arc discharge C-NTs. CVD BN-NTs with improved tribological properties and higher oxidation temperature might be a better candidate than CVD C-NTs for applications in extreme environments.

Sliding on a nanotube: interplay of friction, deformations and structure.

The frictional properties of individual carbon nanotubes (CNTs) are studied by sliding an atomic force microscopy tip across and along its principle axis. This direction-dependent frictional behavior is found to correlate strongly with the presence of structural defects, surface chemistry, and CNT chirality. This study shows that it is experimentally possible to tune the frictional/adhesion properties of a CNT by controlling the CNT structure and surface chemistry, as well as use friction force to predict its structural and chemical properties.