Effects of flow history on extensional rheological properties of wormlike micelle solution.

A wormlike micelle (WLM) solution is a complex fluid that forms when the surfactant concentration is high. It has rheological properties similar to those of polymer solutions. However, unlike polymer molecules, WLM chains possess the dynamic microstructure that can be reversibly broken and reassembled in flows. Therefore, the rheological properties and flow behavior of WLM solutions have attracted much attention owing to their unique dynamic microstructures. However, the effects of the flow history on the extensional rheological properties of WLM solutions remain unclear. In this study, the change in the extensional rheological properties of WLM solutions depending upon on their shear flow histories was investigated by combining the dripping-onto-substrate/capillary break-up extensional rheometry technique with a compressed gas flow (stop-flow) control method. This approach precisely controls the shear flow histories of the WLM solutions. The results revealed that the shear flow history has a substantial impact on elongational rheological properties such as relaxation time. They also showed that the effects of the characteristic shear rate are highly dependent on the surfactant concentration. We expect that the current findings can be applied to understand the extensional rheological properties of complex fluids in industrially relevant processes such as coating and printing.

Quantitative image analysis of the shape and size of circular wound sites generated by vertically stamped scratches.

A protocol for quantitative image analysis of wound generation is important to better understand the integrative process of wound healing and the closure mechanism. Here, we present a method for quantitative analysis of microscopic images of circular wound sites generated by vertically stamped scratches. To demonstrate proof-of-concept validation, we used two types of mechanical stamping tools, a mechanical pencil lead (type 1; brittle) and polydimethylsiloxane (PDMS) pillars (type 2; ductile), to create circular wound sites. We also present a method for analysis of microscopic images of the generated wound sites by suggesting new parameters, such as controlled area transfer ratio, modified shape factor, and roundness index, specifically to investigate the shape and size of wounds via house-coded image processing. We believe that this approach can be potentially useful by providing a better way of studying vertical wound generation for future skin wound generation and care applications compared with its counterpart, conventional horizontal wound generation.

Role of the electric field in selective ion filtration in nanostructures.

Nafion has received great attention as a proton conductor that can block negative ions. Here, we report the effect of a Nafion coating on an anodic aluminium oxide (AAO) nanoporous membrane on its function of ion rejection and filtering depending on the electric field. In our experiments, Nafion, once coated, was used to repel the negative ions (anions) from the coated surface, and then selectively allowed positive ions (cations) to pass through the nanopores in the presence of an electric field. To demonstrate the proof-of-concept validation, we coated Nafion solution onto the surface of AAO membranes with 20 nm nanopores average diameter at different solution concentration levels. Vacuum filtration methods for Nafion coating were vertically applied to the plane of an AAO membrane. An electric field was then applied to the upper surface of the Nafion-coated AAO membrane to investigate if ion rejection and filtering was affected by the presence of the electric field. Both anions and cations could pass through the AAO nanopores without an electric field applied. However, only cations could well pass through the AAO nanopores under an electric field, thus effectively blocking anions from passing through the nanopores. This result shows that ion filtration of electrons has been selectively performed while the system also works as a vital catalyst in reactivating Nafion via electrolysis. A saturated viscosity ratio of Nafion solution for the coating was also determined. We believe that this approach is potentially beneficial for better understanding the fundamentals of selective ion filtration in nanostructures and for promoting the use of nanostructures in potential applications such as ion-based water purification and desalination system at the nanoscale in a massively electrically integrated format.

Mesoscopic perovskite solar cells with an admixture of nanocrystalline TiO2 and Al2O3: role of interconnectivity of TiO2 in charge collection.

Perovskite solar cells with high power conversion efficiency usually employ mesoporous TiO2, however the role of the TiO2 layer has not been clearly resolved. Here we prepared MAPbI3 (MA = CH3NH3) perovskite solar cells with an admixture of nanocrystalline TiO2 and Al2O3 to investigate the role of the mesoporous TiO2 layer. The Al2O3 content was varied from 0% (pure TiO2) to 100% (pure Al2O3) with nominal composition of (1 - x)TiO2 + xAl2O3 (x = 0, 0.25, 0.5, 0.75 and 1). The photocurrent density and fill factor decreased as Al2O3 content increased, whereas the open-circuit voltage was hardly changed. Steady-state photoluminescence (PL) was less quenched as the Al2O3 content increased due to its non-electron-injecting characteristics, where a decrease in PL intensity with increasing TiO2 content was correlated to an increase in photocurrent. Electron injection to TiO2 was also evidenced by time-resolved PL and time-limited photocurrent measurements, where interconnection of TiO2 particles played an important role in charge collection. The slight change in voltage with Al2O3 content was explained by balancing the Fermi position due to a trade-off between charge recombination and the Fermi level. The results observed from the admixture mesoporous layer comprising electron-injecting and electron-non-injecting oxides suggest that electron-injection characteristics play an important role in determining photovoltaic parameters.

Control of I-V hysteresis in CH3NH3PbI3 perovskite solar cell.

Mismatch of current (I)-voltage (V) curves with respect to the scan direction, so-called I-V hysteresis, raises critical issue in MAPbI3 (MA = CH3NH3) perovskite solar cell. Although ferroelectric and ion migration have been proposed as a basis for the hysteresis, origin of hysteresis has not been apparently unraveled. We report here on the origin of I-V hysteresis of perovskite solar cell that was systematically evaluated by the interface-dependent electrode polarizations. Frequency (f)-dependent capacitance (C) revealed that the normal planar structure with the TiO2/MAPbI3/spiro-MeOTAD configuration showed most significant I-V hysteresis along with highest capacitance (10(-2) F/cm(2)) among the studied cell configurations. Substantial reduction in capacitance to 10(-3) F/cm(2) was observed upon replacing TiO2 with PCBM, indicative of the TiO2 layer being mainly responsible for the hysteresis. The capacitance was intensively reduced to 10(-5) F/cm(2) and C-f feature shifted to higher frequency for the hysteresis-free planar structures with combination of PEDOT: PSS, NiO, and PCBM, which underlines the spiro-MeOTAD in part contributes to the hysteresis. This work is expected to provide a key to the solution of the problem on I-V hysteresis in perovskite solar cell.

Highly Reproducible Perovskite Solar Cells with Average Efficiency of 18.3% and Best Efficiency of 19.7% Fabricated via Lewis Base Adduct of Lead(II) Iodide.

High efficiency perovskite solar cells were fabricated reproducibly via Lewis base adduct of lead(II) iodide. PbI2 was dissolved in N,N-dimethyformamide with equimolar N,N-dimethyl sulfoxide (DMSO) and CH3NH3I. Stretching vibration of S═O appeared at 1045 cm(-1) for bare DMSO, which was shifted to 1020 and 1015 cm(-1) upon reacting DMSO with PbI2 and PbI2 + CH3NH3I, respectively, indicative of forming the adduct of PbI2·DMSO and CH3NH3I·PbI2·DMSO due to interaction between Lewis base DMSO and/or iodide (I(-)) and Lewis acid PbI2. Spin-coating of a DMF solution containing PbI2, CH3NH3I, and DMSO (1:1:1 mol %) formed a transparent adduct film, which was converted to a dark brown film upon heating at low temperature of 65 °C for 1 min due to removal of the volatile DMSO from the adduct. The adduct-induced CH3NH3PbI3 exhibited high charge extraction characteristics with hole mobility as high as 3.9 × 10(-3) cm(2)/(V s) and slow recombination rate. Average power conversion efficiency (PCE) of 18.3% was achieved from 41 cells and the best PCE of 19.7% was attained via adduct approach.

Understanding the role of the dye/oxide interface via SnO2-based MK-2 dye-sensitized solar cells.

To understand the role of the dye/oxide interface, a model system using a nanocrystalline SnO2 and 3-hexyl thiophene based MK-2 dye is proposed. A thin interfacial TiO2 blocking layer (IBL) is introduced in between SnO2 and MK-2 and its effects on photocurrent-voltage, electron transport-recombination, and density of states (DOS) are systematically investigated. Compared to the bare SnO2 film, the insertion of IBL leads to a 14-fold improvement in the power conversion efficiency (PCE) despite little change in the dye adsorption amount, which is due to the 7-fold and 2-fold increase in the photocurrent density and voltage, respectively. The charge collection efficiency is substantially improved from 38% to 96% mainly due to the increase in the electron lifetime. The IBL is also found to enhance the dye regeneration efficiency as confirmed by the 15-fold faster dye bleaching recovery dynamics. The recombination resistance increases and the DOS decreases after surface modification of SnO2, which is responsible for the doubly increased voltage. This study suggests that the interfacial layer between the oxide and the dye plays a crucial role in retarding recombination, improving charge collection efficiency, increasing diffusion length, accelerating dye regeneration and narrowing the density of states.

Highly efficient and recyclable nanocomplexed photocatalysts of AgBr/N-doped and amine-functionalized reduced graphene oxide.

Although silver bromide has recently drawn considerable attention because of its high photocatalytic activity, it tends to form agglomerated metallic silver under the irradiation of visible light. Therefore, photocatalytic activity decreases with time and cannot be applied for repeated uses. To overcome this limitation, in the present work, we complexed AgBr with nitrogen doped (N-doped) and amine functionalized reduced graphene oxide (GN). N-doped and/or amine functionalized graphene shows intrinsically good catalytic activity. Besides, amine groups can undergo complexation with silver ions to suppress its reduction to metallic Ag. As a result, these complexed catalysts show excellent photocatalytic activity for the degradation of methylene blue (MB) dye under the irradiation of visible light. Photocatalytic degradation of MB shows that the catalytic activity is optimized at a condition of 0.5 wt % GN, under which ∼99% of MB was degraded only after 50 min of visible light irradiation. Notably, the complexed catalyst is quite stable and retained almost all of its catalytic activity even after greater than 10 repeated cycles. Moreover, the catalyst can also efficiently decompose 2-chlorophenol, a colorless organic contaminant, under visible light exposure. Detailed experimental investigation reveals that hydroxyl (·OH) radicals play an important role for dye degradation reactions. A relevant mechanism for dye degradation has also been proposed.

Growth of CH3NH3PbI3 cuboids with controlled size for high-efficiency perovskite solar cells.

Perovskite solar cells with submicrometre-thick CH(3)NH(3)PbI(3) or CH(3)NH(3)PbI(3-x)Cl(x) active layers show a power conversion efficiency as high as 15%. However, compared to the best-performing device, the average efficiency was as low as 12%, with a large standard deviation (s.d.). Here, we report perovskite solar cells with an average efficiency exceeding 16% and best efficiency of 17%. This was enabled by the growth of CH(3)NH(3)PbI(3) cuboids with a controlled size via a two-step spin-coating procedure. Spin-coating of a solution of CH(3)NH(3)I with different concentrations follows the spin-coating of PbI(2), and the cuboid size of CH(3)NH(3)PbI(3) is found to strongly depend on the concentration of CH(3)NH(3)I. Light-harvesting efficiency and charge-carrier extraction are significantly affected by the cuboid size. Under simulated one-sun illumination, average efficiencies of 16.4% (s.d. ± 0.35), 16.3% (s.d. ± 0.44) and 13.5% (s.d. ± 0.34) are obtained from solutions of CH(3)NH(3)I with concentrations of 0.038 M, 0.050 M and 0.063 M, respectively. By controlling the size of the cuboids of CH(3)NH(3)PbI(3) during their growth, we achieved the best efficiency of 17.01% with a photocurrent density of 21.64 mA cm(-2), open-circuit photovoltage of 1.056 V and fill factor of 0.741.

Hierarchical SnO2 nanoparticle-ZnO nanorod photoanode for improving transport and life time of photoinjected electrons in dye-sensitized solar cell.

A hierarchical photoanode comprising a SnO(2) nanoparticle underlayer and a ZnO nanorod overlayer was prepared and its photovoltaic performance was compared to photoanodes consisting of SnO(2) nanoparticle only and ZnO nanorod only. The photoanode layer thickness was adjusted to about 7.6 µm to eliminate thickness effect. Ruthenium complex, coded N719, was used as a sensitizer. The photoanode composed of ZnO nanorod only showed a power conversion efficiency (PCE) as low as 0.54% with a short-circuit photocurrent density (J(SC)) of 2.04 mA/cm(2) and an open-circuit voltage (V(OC)) of 500 mV. The photoanode with SnO(2) nanoparticle only exhibited higher PCE (1.24%) because of higher J(SC) (6.64 mA/cm(2)), whereas V(OC) (340 mV) was lower than ZnO nanorod. Compared to SnO(2) nanoparticle and ZnO nanorod films, the bilayer structured film demonstrated much higher PCE (2.62%) because of both higher J(SC) (7.35 mA/cm(2)) and V(OC) (660 mV). Introduction of ZnO nanorod on the SnO(2) nanoparticle layer improved significantly electron transport and lifetime compared to the SnO(2) only film. One Order of magnitude slower charge recombination rate for the bilayer film than for the SnO(2) film was mainly responsible for the improved efficiency.

Improvement of mass transport of the [Co(bpy)3](II/III) redox couple by controlling nanostructure of TiO2 films in dye-sensitized solar cells.

Mass transport of the [Co(bpy)(3)](II/III) redox electrolyte is found to strongly depend on porosity and pore size of mesoporous TiO(2) films. Photocurrent density is improved by nearly two times with increasing the porosity from 0.52 to 0.59 despite 23% decreased dye loading. Optimized nanostructure sensitized with MK-2 dye shows efficiency of 5.5% at 1 sun.

Pseudo first-order adsorption kinetics of N719 dye on TiO2 surface.

We have investigated the adsorption kinetics of Ru-based N719 dye on TiO(2) surface in dye-sensitized solar cell using 0.5 mM and 5 mM dye solutions. The amount of adsorbed dye on TiO(2) surface of ca. 5 µm-thick film was measured as a function of immersion (adsorption) time. The amount of adsorbed dye increases with increasing the adsorption time and keeps constant after saturation. Completion of dye adsorption is found to be more than 5 times faster in 5 mM than in 0.5 mM. Since the change of dye concentration is negligible compared to that of number of TiO(2) adsorption site, reaction order and rate constant can be estimated from a pseudo reaction. Among the zeroth-, first-, and second-order simulation, the observed data follow first order reaction for both 0.5 mM and 5 mM cases. The rate constant is estimated to be 0.504 min(-1) for 5 mM and 0.094 min(-1) for 0.5 mM, which indicates that completion of dye adsorption is about 5 times shorter in 5 mM than in 0.5 mM. This is consistent with the observed adsorption time difference. Except for the difference in adsorption kinetics, best cell efficiency is similar regardless of dye solution concentration.

Anthocyanin accumulation and expression of anthocyanin biosynthetic genes in radish (Raphanus sativus).

Radish [Raphanus sativus (Rs)] is an important dietary vegetable in Asian countries, especially China, Japan, and Korea. To elucidate the molecular mechanisms of anthocyanin accumulation in radish, the gene expression of enzymes directly involved in anthocyanin biosynthesis was analyzed. These genes include phenylalanine ammonia lyase (PAL), cinnamate 4-hydroxylase (C4H), 4-coumarate-CoA ligase (4CL), chalcone synthase (CHS), chalcone isomerase (CHI), flavanone 3-hydroxylase (F3H), dihydroflavonol reductase (DFR), and anthocyanidin synthase (ANS). RsDFR and RsANS were found to accumulate in the flesh or skin of two radish cultivars (Man Tang Hong and Hong Feng No.1). Radish skin contained higher CHS, CHI, and F3H transcript levels than radish flesh in all three cultivars. In the red radish, 16 anthocyanins were separated and identified by high-performance liquid chromatography (HPLC) and elctrospray ionization-tandem mass spectrometry (ESI-MS/MS). Some of them were acylated with coumaroyl, malonoyl, feruoyl, and caffeoyl moieties. Furthermore (-)-epicatechin and ferulic acid were also identified in the three cultivars.