Nanoscale Mapping of Molecular Vibrational Modes via Vibrational Noise Spectroscopy.

We have developed a "vibrational noise spectroscopy (VNS)" method to identify and map vibrational modes of molecular wires on a solid substrate. In the method, electrical-noises generated in molecules on a conducting substrate were measured using a conducting atomic force microscopy (AFM) with a nanoresolution. We found that the bias voltage applied to the conducting AFM probe can stimulate specific vibrational modes of measured molecules, resulting in enhanced electrical noises. Thus, by analyzing noise-voltage spectra, we could identify various vibrational modes of the molecular wires on the substrates. Further, we could image the distribution of vibrational modes on molecule patterns on the substrates. In addition, we found that VNS imaging data could be further analyzed to quantitatively estimate the density of a specific vibrational mode in the layers of different molecular species. The VNS method allows one to measure molecular vibrational modes under ambient conditions with a nanoresolution, and thus it can be a powerful tool for nanoscale electronics and materials researches 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.

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 mapping of edge-state conductivity and charge-trap activity in topological insulators.

We report the nanoscale mapping of topological edge-state conductivity and the effects of charge-traps on conductivity in a Bi2Se3 multilayer film under ambient conditions. In this strategy, we applied an electric field perpendicular to the surface plane of Bi2Se3via a conducting probe to directly map the charge-trap densities and conductivities with a nanoscale resolution. The results showed that edge regions had one-dimensional characteristics with higher conductivities (two orders) and lower charge-trap densities (four orders) than those of flat surface regions where their conductivities and charge-traps were dominated by bulk effects. Additionally, edges showed an enhanced conductivity with an elevated electric field, possibly due to the creation of new topological states by stronger spin-Hall effects. Importantly, we observed ultra-high photoconductivity predominantly on edge regions compared with that of flat surface regions, which was attributed to the excitation of edge-state carriers by light. Since our method provides an important insight into the charge transport in topological insulators, it could be a significant advancement in the development of error-tolerant topotronic devices.

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.

Electronic Traps and Their Correlations to Perovskite Solar Cell Performance via Compositional and Thermal Annealing Controls.

Herein, underlying factors for enabling efficient and stable performance of perovskite solar cells are studied through nanostructural controls of organic-inorganic halide perovskites. Namely, MAPbI3, (FA0.83MA0.17)Pb(I0.83Br0.17)3, and (Cs0.10FA0.75MA0.15)Pb(I0.85Br0.15)3 perovskites (abbreviated as MA, FAMA, and CsFAMA, respectively) are examined with a grain growth control through thermal annealing. FAMA- and CsFAMA-based cells result in stable photovoltaic performance, while MA cells are sensitively dependent on the perovskite grain size dominated by annealing time. Micro-/nanoscopic features are comprehensively analyzed to unravel the origin that is directly correlated to the cell performance with the applications of electronic-trap characterizations such as photoconductive noise microscopy and capacitance analyses. It is revealed that CsFAMA has a lower trap density compared to MA and FAMA through the analyses of 1/ f noises and trapping/detrapping capacitances. Also, an open-circuit voltage ( Voc) change is correlated to the variation of trap states during the shelf-life test: FAMA and CsFAMA cells with the negligible change of Voc over weeks exhibit trap states shifting toward the band edge, although the power-conversion efficiencies are clearly reduced. The origins that critically affect the solar cell performance through the characterizations of shallow/deep traps with additional mobile defects in the perovskite and interfaces are discussed.

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.

Nanoscale direct mapping of localized and induced noise sources on conducting polymer films.

The localized noise-sources and those induced by external-stimuli were directly mapped by using a conducting-AFM integrated with a custom-designed noise measurement set-up. In this method, current and noise images of a poly(9,9-dioctylfluorene)-polymer-film on a conducting-substrate were recorded simultaneously, enabling the mapping of the resistivity and noise source density (NT). The polymer-films exhibited separate regions with high or low resistivities, which were attributed to the ordered or disordered phases, respectively. A larger number of noise-sources were observed in the disordered-phase-regions than in the ordered-phase regions, due to structural disordering. Increased bias-voltages on the disordered-phase-regions resulted in increased NT, which is explained by the structural deformation at high bias-voltages. On photo-illumination, the ordered-phase-regions exhibited a rather large increase in the conductivity and NT. Presumably, the illumination released carriers from deep-traps which should work as additional noise-sources. These results show that our methods provide valuable insights into noise-sources and, thus, can be powerful tools for basic research and practical applications of conducting polymer films.

Nanoscale Direct Mapping of Noise Source Activities on Graphene Domains.

An electrical noise is one of the key parameters determining the performance of modern electronic devices. However, it has been extremely difficult, if not impossible, to image localized noise sources or their activities in such devices. We report a "noise spectral imaging" strategy to map the activities of localized noise sources in graphene domains. Using this method, we could quantitatively estimate sheet resistances and noise source densities inside graphene domains, on domain boundaries and on the edge of graphene. The results show high activities of noise sources and large sheet resistance values at the domain boundary and edge of graphene. Additionally, we showed that the top layer in double-layer graphene had lower noises than single-layer graphene. This work provides valuable insights about the electrical noises of graphene. Furthermore, the capability to directly map noise sources in electronic channels can be a major breakthrough in electrical noise research in general.

Evaluating the Optoelectronic Quality of Hybrid Perovskites by Conductive Atomic Force Microscopy with Noise Spectroscopy.

Organic-inorganic hybrid perovskite solar cells have emerged as promising candidates for next-generation solar cells. To attain high photovoltaic efficiency, reducing the defects in perovskites is crucial along with a uniform coating of the films. Also, evaluating the quality of synthesized perovskites via facile and adequate methods is important as well. Herein, CH3NH3PbI3 perovskites were synthesized by applying second solvent dripping to nonstoichiometric precursors containing excess CH3NH3I. The resulting perovskite films exhibited a larger average grain size with a better crystallinity compared to that from stoichiometric precursors. As a result, the performance of planar perovskite solar cells was significantly improved, achieving an efficiency of 14.3%. Furthermore, perovskite films were effectively analyzed using a conductive AFM and noise spectroscopy, which have been uncommon in the field of perovskite solar cells. Comparing the topography and photocurrent maps, the variation of photocurrents in nanoscale was systematically investigated, and a linear relationship between the grain size and photocurrent was revealed. Also, noise analyses with a conductive probe enabled examination of the defect density of perovskites at specific grain interiors by excluding the grain-boundary effect, and reduced defects were clearly observed for the perovskites using CH3NH3I-rich precursors.