Nanoscale Mapping of Carrier Mobilities in the Ballistic Transports of Carbon Nanotube Networks.

Much progress has been made in the nanoscale analysis of nanostructures, while the mapping of key charge transport properties such as a carrier mobility remains a challenge, especially for one-dimensional systems. Here, we report the nanoscale mapping of carrier mobilities in carbon nanotube (CNT) networks and show that charge transport behaviors varied depending on network structures. In this work, the spatial distribution of localized charge transport properties such as mobilities and charge trap densities in CNT networks were mapped via a scanning noise microscopy. The mobility map was obtained from the conductivity maps measured at different back-gate biases, showing up to two orders of mobility variations depending on localized network structures. Furthermore, from the maps, correlations between mobility/conductivity and charge trap density were analyzed to determine charge transport mechanisms. In metallic CNT networks, the regions with rather high (low) or low (high) charge trap densities (mobilities) exhibited a diffusive or ballistic transport behavior, respectively. Interestingly, semiconducting CNT networks also exhibited a gradual transition from a diffusive to a ballistic transport behavior as the CNT mobility was increased by reaching the on-state with negative gate biases. The mapping of the cross-patterned CNT network showed that metallic CNT electrodes could achieve a good electrical contact with semiconducting CNTs without high contact resistance regions. Since this method allowed one to map versatile charge transport properties such as mobility, conductivity, and charge trap density, it can be a powerful tool for basic research about charge transport phenomena and practical device applications.

Dipolar Noise in Fluorinated Molecular Wires.

We demonstrate a strategy to directly map and quantify the effects of dipole formation on electrical transports and noises in the self-assembled monolayers (SAMs) of molecular wires. In this method, the SAM patterns of fluorinated molecules with dipole moments were prepared on conducting substrates, and a conducting probe in contact-mode atomic force microscopy was utilized to map currents and noises through the probe on the molecular patterns. The maps were analyzed to extract the characteristic parameters of dipolar noises in SAMs, and the results were compared with those of hydrogenated molecular patterns without dipole moments. At rather low bias conditions, the fluorinated molecular junctions exhibited a tunneling conduction and a resistance value comparable to that of the hydrogenated molecules with a six-times-longer length, which was attributed to stronger dipoles formation in fluorinated molecules. Interestingly, conductance (G) in different regions of fluorinated molecular patterns exhibited a strong correlation with a noise power spectral density of SI/I2 like SI/I2 ∝ G-2, which can be explained by enhanced barrier fluctuations produced by the dipoles of fluorinated molecules. Furthermore, we observed that the noise power spectral density of fluorinated molecules showed an anomalous frequency (f) dependence like SI/I2 ∝ 1/f1.7, possibly due to the slowing down of the tunneling of carriers from increased barrier fluctuations. In rather high bias conditions, conductions in both hydrogenated and fluorinated molecules showed a transition from tunneling to thermionic charge transports. Our results provide important insights into the effects of dipoles on mesoscopic transport and resistance-fluctuation in molecules and could have a significant impact on the fundamental understanding and applications in this area.

Long-Range Order Self-Assembly of Conjugated Block Copolymers at Inclined Air-Liquid Interfaces.

Here, we report that long-range order, direction-controlled, ultrathin conjugated polymer films can be formed by the self-assembly of conjugated block copolymers (i.e., poly(3-hexylthiophene)-block-poly(ethylene glycol)) at inclined air-water interfaces. Structure analyses revealed well-aligned nanowire arrays of poly(3-hexylthiophene) with a dramatically increased ordered domain size compared to the polymer films formed on a flat water surface. The improved degree of order was attributed to the flow field created by the enhanced solvent evaporation at the top of the water contact line. Note that it is challenging to prepare such well-ordered and molecularly thin films of conjugated polymers by conventional fabrication methods. The long-range order polymer film showed hole mobility an order of magnitude higher than polymer films formed on a flat interface when implemented as an active layer of field-effect transistor devices. This study demonstrates that a simple interface modification can significantly impact the self-assembly process, structure, and function of polymer films formed at the air-liquid interface.

Binary Self-Assembly of Conjugated Block Copolymers and Quantum Dots at the Air-Liquid Interface into Ordered Functional Nanoarrays.

Controlling the nanoscale morphology of conducting polymer/nanoparticle hybrid films is a highly desired but challenging task. Here, we report that such functional hybrid films with unprecedented structural order can be formed through the self-assembly of conjugated block copolymers and CdSe quantum dots at the air-water interface. The one-step assembly of quantum dots and block copolymers composed of polythiophene and polyethylene glycol (P3HT-b-PEG) at the fluidic interface generated a highly ordered assembly structure of P3HT nanowires and one-dimensional quantum dot arrays. Structure analyses revealed a unique self-assembly behavior and size dependency, which are distinct from the conventional self-assembly of coil-type polymers on solid substrates. Interestingly, hydrophobic quantum dots reside at the interface between P3HT and PEG domains without disrupting the P3HT packing structure, which is advantageous for the optoelectronic properties. Furthermore, large particles bridge the P3HT nanowires at both ends, while small particles decorate each P3HT/PEG interfaces, thus forming tight p-n junctions for a broad size range of nanoparticles. The nanoparticle-incorporated hybrid films showed more than an order of magnitude higher photocurrent and light sensitivity compared to polymer-only films, consistent with the assembly structure with close contact between the organic and inorganic semiconductors.

Nanoscale enhancement of photoconductivity by localized charge traps in the grain structures of monolayer MoS2.

We report a method for mapping the nanoscale anomalous enhancement of photoconductivity by localized charge traps in the grain structures of a molybdenum disulfide (MoS2) monolayer. In this work, a monolayer MoS2 film was laterally scanned by a nanoscale conducting probe that was used to make direct contact with the MoS2 surface. Electrical currents and noise maps were measured through the probe. By analyzing the data, we obtained maps for the sheet resistance and charge trap density for the MoS2 grain structures. The maps clearly show grains for which sheet resistance and charge trap density were lower than those of the grain boundaries. Interestingly, we found an unusual inverse proportionality between the sheet resistance and charge trap density in the grains, which originated from the unique role of sulfur vacancies acting as both charge hopping sites and traps in monolayer MoS2. In addition, under light illumination, the larger the trap density of a region was, the larger the photocurrent of the region was, indicating anomalous enhancement of the photocurrent by traps. Since our method provides valuable insights to understand the nanoscale effects of traps on photoconductive charge transport, it can be a powerful tool for noise studies and the practical application of two-dimensional materials.

Human-like smelling of a rose scent using an olfactory receptor nanodisc-based bioelectronic nose.

We report a strategy for the human-like smelling of a rose scent utilizing olfactory receptor nanodisc (ND)-based bioelectronic nose devices. In this strategy, a floating electrode (FE)-based carbon nanotube (CNT) field effect transistor (FET) was functionalized with human olfactory receptor 1A2 (hOR1A2)-embedded NDs (hOR1A2NDs). The hOR1A2NDs responded to rose scent molecules specifically, which were monitored electrically using the underlying CNT-FET. This strategy allowed us to quantitatively assess the contents of geraniol and citronellol, the main components of a rose scent, as low as 1 fM and 10 fM, respectively. In addition, it enabled us to selectively discriminate a specific rose odorant from other odorants. Significantly, we also demonstrated that the responses of hOR1A2NDs to a rose scent could be strongly enhanced by enhancer materials like a human nose. Furthermore, the method provided a means to quantitatively evaluate rose scent components in real samples such as rose oil. Since our method allows one to quantitatively evaluate general rose scent ingredients just like a human nose, it could be a powerful strategy for versatile basic research and various applications such as fragrance development.

Nanoscale anomalous noise source switching with a trap-free current transition in a PEDOT:PSS film.

We imaged localized charge traps in a PEDOT:PSS film by using a scanning noise microscopy (SNM) system and observed anomalous noise source switching behaviors affecting the electrical characteristics of the film. The SNM system enabled us to measure the localized electrical current and noise maps of a PEDOT:PSS film with nanoscale resolution. The measured maps of the currents and noises were utilized to calculate effective charge trap densities in the film. As a result, we found non-homogeneous distributions of currents and effective charge trap densities on the localized area of the film due to the non-uniform distribution of PEDOT-rich and PSS-rich grains. At a low bias voltage, we observed high current levels and high charge trap densities in PEDOT-rich grains, while PSS-rich grains showed low-current levels and charge trap densities. Interestingly, the charge trap densities in both grains showed a noise source switching behavior with respect to the applied bias voltages, and the behavior strongly affected their electrical characteristic such as the trap-free transition of currents. These results indicate that the charge traps in a PEDOT:PSS film play an important role in the electrical characteristics of the films. Our observations provide a valuable insight on the understanding of the electrical characteristics of PEDOT:PSS films and an important guideline for its practical applications.

Mapping reversible photoswitching of molecular resistance fluctuations during the conformational transformation of azobenzene-terminated molecular switches.

We report a direct mapping and analysis of electrical noise in azobenzene-terminated molecular monolayers, revealing reversible photoswitching of the molecular resistance fluctuations in the layers. In this work, a conducting atomic force microscope combined with a homemade spectrum analyzer was used to image electrical current and noise at patterned self-assembled monolayers (SAMs) of azobenzene-terminated molecular wires on a gold substrate. We analyzed the current and noise imaging data to obtain maps of molecular resistances and amount of mean-square fluctuations in the resistances of the regions of trans-azobenzene and a cis/trans-azobenzene mixture. We revealed that the fluctuations in the molecular resistances in the SAMs were enhanced after the trans-to-cis isomerization, while the resistances were reduced. This result could be attributed to enhanced disorders in the molecular arrangements in the cis-SAMs. Furthermore, we observed that the changes in the resistance fluctuations were reversible with respect to repeated trans-to-cis and cis-to-trans isomerizations, indicating that the effects originated from reversible photoswitching of the molecular structures rather than irreversible damages of the molecules. These findings provide valuable insights into the electrical fluctuations in photoswitchable molecules, which could be utilized in further studies on molecular switches and molecular electronics in general.

Nanoscale "Noise-Source Switching" during the Optoelectronic Switching of Phase-Separated Polymer Nanocomposites.

A method is developed to directly map nanoscale "noise-source switching" phenomena during the optoelectronic switching of phase-separated polymer nanocomposites of tetrathiafulvalene (TTF) and phenyl-C61 -butyric acid methyl ester (PCBM) molecules dispersed in a polystyrene (PS) matrix. In the method, electrical current and noise maps of the nanocomposite film are recorded using a conducting nanoprobe, enabling the mapping of a conductivity and a noise-source density. The results provide evidence for a repeated modulation in noise sources, a "noise-source switching," in each stage of a switching cycle. Interestingly, when the nanocomposite is "set" by a high bias, insulating PS-rich phases shows a drastic decrease in a noise-source density which becomes lower than that of conducting TTF-PCBM-rich phases. This can be attributed to a trap filling by charge carriers generated from a TTF (donor)-PCBM (acceptor) complex. In addition, when the film is exposed to UV, an optical switching occurs due to chemical reactions which lead to irreversible changes on the noise-source density and conductivity. The method provides a new insight on noise-source activities during the optoelectronic switching of polymer nanocomposites and thus can be a powerful tool for basic noise research and applications in organic memory devices.

Mapping nanoscale effects of localized noise-source activities on photoconductive charge transports in polymer-blend films.

We develolped a method to directly image the nanoscale effects of localized noise-source activities on photoconducting charge transports in domain structures of phase-separated polymer-blend films of Poly(9,9-di-n-octylfluorenyl-2,7-diyl) and Poly(9,9-di-n-octylfluorene-alt-benzothiadiazole). For the imaging, current and noise maps of the polymer-blend were recorded using a conducting nanoprobe in contact with the surface, enabling the conductivity (σ) and noise-source density (N T) mappings under an external stimulus. The blend-films exhibited the phase-separation between the constituent polymers at domains level. Within a domain, high σ (low N T) and low σ (high N T) regions were observed, which could be associated with the ordered and disordered regions of a domain. In the N T maps, we observed that noise-sources strongly affected the conduction mechanism, resulting in a scaling behavior of σ âˆ [Formula: see text] in both ordered and disordered regions. When a blend film was under an influence of an external stimulus such as a high bias or an illumination, an increase in the σ was observed, but that also resulted in increases in the N T as a trade-off. Interestingly, the Δσ versus ΔN T plot exhibited an unusual scaling behavior of Δσ âˆ [Formula: see text] which is attributed to the de-trapping of carriers from deep traps by the external stimuli. In addition, we found that an external stimulus increased the conductivity at the interfaces without significantly increasing their N T, which can be the origin of the superior performances of polymer-blend based devices. These results provide valuable insight about the effects of noise-sources on nanoscale optoelectronic properties in polymer-blend films, which can be an important guideline for improving devices based on polymer-blend.

Air-Liquid Interfacial Self-Assembly of Non-Amphiphilic Poly(3-hexylthiophene) Homopolymers.

Here, we demonstrate that the self-assembly of poly(3-hexylthiophene) (P3HT) at the air-water interface can lead to free-standing films of densely packed P3HT nanowires. Interfacial self-assembly on various liquid subphases, such as water, diethylene glycol, and glycerol, indicates that the viscosity of the subphase is an important factor for the formation of well-ordered nanostructures. The thin-film morphology is also sensitive to the concentration of P3HT, its molecular weight (MW), and the presence of oxidative defects. The densely packed nanowire films can be easily transferred to solid substrates for device applications. The ultrathin films of P3HT prepared by the interfacial assembly showed significantly higher hole mobility (∼3.6 × 10-2 cm2/V s) in a field-effect transistor than comparably thin spin-cast films. This work demonstrates that the air-liquid interfacial assembly is not limited to amphiphilic polymers and can, under optimized conditions, be applied to fabricate ultrathin films of widely used conjugated polymers with controlled morphologies.

Direct mapping of electrical noise sources in molecular wire-based devices.

We report a noise mapping strategy for the reliable identification and analysis of noise sources in molecular wire junctions. Here, different molecular wires were patterned on a gold substrate, and the current-noise map on the pattern was measured and analyzed, enabling the quantitative study of noise sources in the patterned molecular wires. The frequency spectra of the noise from the molecular wire junctions exhibited characteristic 1/f2 behavior, which was used to identify the electrical signals from molecular wires. This method was applied to analyze the molecular junctions comprising various thiol molecules on a gold substrate, revealing that the noise in the junctions mainly came from the fluctuation of the thiol bonds. Furthermore, we quantitatively compared the frequencies of such bond fluctuations in different molecular wire junctions and identified molecular wires with lower electrical noise, which can provide critical information for designing low-noise molecular electronic devices. Our method provides valuable insights regarding noise phenomena in molecular wires and can be a powerful tool for the development of molecular electronic devices.