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

Development of Self-Organizing, Self-Directing Molecular Nanowires: Synthesis and Characterization of Conjoined DNA−2,5-Bis(2-thienyl)pyrrole Oligomers

Specifically designed conducting polymers were prepared from monomers that are covalently linked to duplex DNA. These materials combine the self-assembly properties of DNA with those of conducting polymers and may be valuable in the development of self-directing molecular nanowires. Single-strand DNA oligomers having 2,5-bis(2-thienyl)pyrroles (SNS monomers) covalently linked at every other nucleobase along one strand form stable duplexes with their complementary strands. The duplex DNA serves as a scaffold that aligns the SNS monomers within its major groove. The reaction of these SNS-containing duplexes with horseradish peroxidase and H2O2 (an oxidant) results in the conversion of the SNS monomers to a conjoined (covalently linked) polymer having the optical properties of a conducting polymer. Examination of radiolabeled oligomers confirms bond formation between SNS monomers, and that conclusion is supported by AFM images. The conjoined polymers have structures that are determined and controlled by the DNA template

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

Influence of structural disorder on the elastic, frictional, and electrical properties in functionalized polyaniline thin films at the nanoscale investigated by atomic force microscopy

We investigated the influence of structural order on the elastic, frictional, and electrical properties of butylthio-functionalized PANI (PANI-SBu) films by atomic force microscopy (AFM)-based techniques, including PeakForce quantitative nanomechanical mapping, friction force microscopy, and conductive AFM. The PANI-SBu films were prepared by the drop-cast method from the solution of PANI-SBu in N-methyl-2-pyrrolidone that was continuously stirred. The PANI-SBu films were fabricated after different solution stirring times. The shear force during the mechanical stir will disentangle the highly-coiled PANI-SBu polymer chains in the solution. Therefore, the polymer chains in solution cast on the substrates will progressively self-assemble into a more organized structure when solvents evaporate, leading to PANI-SBu films with improved structural order. Our AFM studies discovered that more structurally-ordered PANI-SBu films have substantially larger out-of-plane elastic moduli and charge mobility but smaller kinetic friction coefficients. The denser packing of polymer molecules increases film elasticities and promotes chain-to-chain charge transport. In addition, stiffer PANI-SBu film surfaces are more difficult to deform when sheared by the sliding AFM probe, resulting in less energy dissipation during AFM friction measurements. Thus, smaller kinetic friction coefficients were found. Conversely, more structurally-disordered PANI-SBu films have smaller elasticity and charge mobility but larger kinetic friction coefficients. Our results demonstrate that it is possible to manipulate the elastic, frictional, and electrical properties of PANI-SBu films by controlling their structural order, which can be essential for developing polymer-based composite materials and flexible electronic devices.</p

Photoluminescence Enhancement in WS₂ Nanosheets Passivated with Oxygen Ions: Implications for Selective Area Doping

The dominant defect types in chemical-vapor-deposited (CVD) tungsten disulfide (WS2) monolayers (ML) were regulated through mask-assisted scattered-oxygen-ion (O+) implantation. A shadow mask allowed for two distinctive implantation regions: directly bombarded and mask-shaded. Upon direct implantation, photoluminescence (PL) was universally suppressed, whereas in the mask-shaded region, PL was enhanced by up to 500% at low doses before suppression at doses of >3 × 1013 ions/cm2. We verified that the introduction of scattered O+ ions and low-density structural atomic defects are the two prerequisites for PL enhancement by replacing O+ ions with C+ ions and eliminating the involvement of physisorbed gases or laser treatment. Density functional theory calculations were carried out, suggesting a possible mechanism for the vacancy-induced dangling bonds in WS2. Sulfur- or tungsten-related vacancies create in-gap deep trap states, hindering electron–hole recombination. Scattered-oxygen treatment passivates these sulfur vacancies by effectively eliminating these in-gap nonradiative pathways. In addition, it further increases the transition probability by creating more tungsten-dominated states near the conduction band edge through charge transfer. This work demonstrates a facile and successful single-step method to passivate sulfur vacancies with scattered oxygen ions. It has the potential to heal the PL quenching that originated from the intrinsic high defect density in a CVD-grown WS2 ML