Exploring the Role of Central Metals in Bulky Phthalocyanines for Dye-Sensitized Solar Cells.

Two series of metallo-(Zn(II), Mg(II), and Ru(II)) and free-base phthalocyanines (Pcs) with a carboxyl anchoring group and well-established bulky peripheral substituents (either tert-butyl or bulky 2,6-diisopropylphenoxy) were synthesized and tested as sensitizers in dye-sensitized solar cells (DSSCs). The trend of photovoltaic efficiencies (PCEs) for free-base and metallo Pcs followed the order Zn(II)Pc>Mg(II)Pc≫H2Pc ≈ Ru(II)Pc regardless of the peripheral substitution. Higher efficiencies (4.95 versus 3.63 for the Zn(II) derivatives) were achieved with Pcs bearing the bulkier 2,6-diisopropylphenoxy group, indicating a lower aggregation and more suitable HOMO-LUMO levels. Furthermore, these derivatives showed a morelevant influence of the metal on the PCE values (from the highest 4.95 for the Zn(II)Pc to the lowest 0.23 for the Ru(II)Pc. In both series, the best PCEs observed with the Zn(II) derivatives were mainly due to their highest Jsc values. The lowest efficiencies found for the free-bases and Ru(II) derivatives were attributed to a mismatch between their LUMO levels and the conduction band of the TiO2,and lower light-harvesting capabilities, respectively. In conclusion, Zn(II) derivatives are still the best Pc candidates to use as sensitizers in molecular photovoltaics.

Non-Markovian effects of conformational fluctuations on the global diffusivity in Langevin equation with fluctuating diffusivity.

Local diffusivity of a protein depends crucially on the conformation, and the conformational fluctuations are often non-Markovian. Here, we investigate the Langevin equation with non-Markovian fluctuating diffusivity, where the fluctuating diffusivity is modeled by a generalized Langevin equation under a double-well potential. We find that non-Markovian fluctuating diffusivity affects the global diffusivity, i.e., the diffusion coefficient obtained by the long-time trajectories when the memory kernel in the generalized Langevin equation is a power-law form. On the other hand, the diffusion coefficient does not change when the memory kernel is exponential. More precisely, the global diffusivity obtained by a trajectory whose length is longer than the longest relaxation time in the memory kernel is not affected by the non-Markovian fluctuating diffusivity. We show that these non-Markovian effects are the consequences of an everlasting effect of the initial condition on the stationary distribution in the generalized Langevin equation under a double-well potential due to long-term memory.

The Long and Bright Path of a Lanthanide MOF: From Basics towards the Application.

The development of portable, reliable, and low-cost sensors for assessing the quality of natural water sources is of high relevance in developing countries as they can serve as an intermediate solution prior to the building of permanent potable water distribution infrastructure. These sensors should be simple to operate by non-trained operators and easy to manufacture locally. Lanthanide-based metal-organic frameworks (MOFs) offer a trustable platform due to their intense emission in regions of the visible spectra and their high sensitivity to fluorides in water. Cotton was chosen as a substrate due to its high hydrophilicity which, together with the highly porous nature of the MOF, allows for shorter reaction times. The modified cotton was characterized by XRD, SEM as well as XAFS, hence probing the presence of [Tb(BTC)6 (H2 O)] (Tb-BTC) attachment to cotton. Changes in the emission when Tb-BTC modified cotton was exposed to water and aqueous fluoride solutions were monitored as a function of time. Crystalline phase changes were identified that correlated to structural information. Finally, the Tb-BTC modified cotton was used to build a fluoride demonstrator sensor with a linear response of up to 10 mg L-1 and a limit of detection of 0.8 mg L-1 , making it suitable for drinking water analysis under international regulations.

Stacking Control by Molecular Symmetry of Sterically Protected Phthalocyanines.

The synthesis and characterization of two phthalocyanine (Pc) structural isomers, 1 and 2, in which four 2,6-di(hexyloxy)phenyl units were attached directly to the 1,8,15,22- or 1,4,15,18-positions of the Pc rings, are described. Both Pcs 1 and 2 exhibited low melting points, i.e., 120 and 130 °C respectively, due to the reduction in intermolecular π-π interaction among the Pc rings caused by the steric hindrance of 2,6-dihexyloxybenzene units. The thermal behaviors were investigated with temperature-controlled polarizing optical microscopy, differential scanning calorimetry, powder X-ray diffraction, and absorption spectral analyses. Pc 1, having C4h molecular symmetry, organized into a lamellar structure containing lateral assemblies of Pc rings. In contrast, the other Pc 2 revealed the formation of metastable crystalline phases, including disordered stacks of Pcs due to rapid cooling from a melted liquid.

Increased Light-Harvesting in Dye-Sensitized Solar Cells through Förster Resonance Energy Transfer within Supramolecular Dyad Systems.

Novel pyridine-substituted subphthalocyanines were prepared for an additional harvesting of a green spectral region of the solar light spectrum for zinc phthalocyanine-based dye-sensitized solar cells. These compounds can bind with the central metal of zinc phthalocyanines to form the corresponding supramolecular complexes as monitored by the absorption and fluorescence spectral changes. The stability constants of these complexes were altered by the number and position of pyridine units in the pyridine-substituted subphthalocyanines. On the basis of fluorescence titration study, the complexes efficiently transfer energy from the subphthalocyanine to zinc phthalocyanine. The solar cells using TiO2 electrodes stained with the supramolecular complexes, composed of zinc phthalocyanine sensitizer and pyridine-substituted subphthalocyanines, showed panchromatic responses, and the photocurrent generation in the range of 500-600 nm is attributed to the efficient Förster resonance energy transfer from subphthalocyanine to zinc phthalocyanine on the TiO2 surface.

Regioregular Phthalocyanines Substituted with Bulky Donors at Non-Peripheral Positions.

Three regioregular phthalocyanines (1-3) were synthesized selectively by the cyclic tetramerization of phthalonitriles bearing a bulky diarylamine substituent at the next position of nitrile. The steric repulsion at the tetramerization of bulky phthalonitriles allowed for the selective formation of regioregular phthalocyanines as confirmed by NMR and single crystal X-ray structural analyses. The absorption spectrum of 1 substituted with di(4-tert-butylphenyl)amine groups at the non-peripheral positions showed a non-split Q-band at 764 nm, which was redshifted by 83 nm compared with that of metal free phthalocyanine (H2 Pc). The TD-DFT calculation and electrochemical studies prove that the substitution of diarylamine groups at the α-positions effectively destabilizes the HOMO energy level, which causes a large redshift of the Q-band. Moreover, 1 can generate a one-electron oxidation species through chemical oxidation. The Q-band position of 2 bearing 4,4'-dimetoxyphenylamine units was further shifted by 10 nm compared with that of 1. In addition, 3 having carbazole units showed a small redshift of the Q-band relative to H2 Pc. The hole-mobility of 2 in thin film was determined to be 1.1×10-5  cm V-1 s-1 by using a space charge limited current method. A perovskite solar cell employing 2 as a hole-transporting layer gave an efficiency of 5.1 % under standard global 100 Wcm-2 AM 1.5 G illumination.

Low-Symmetry Ω-Shaped Zinc Phthalocyanine Sensitizers with Panchromatic Light-Harvesting Properties for Dye-Sensitized Solar Cells.

Two low-symmetry phthalocyanines (Pcs) substituted with thiophene units at the non-peripheral (α) and peripheral (ß) positions were synthesized and their optical, electronic-structure, and electrochemical properties were investigated. The substitution of thiophene units at the α positions of the phthalocyanine skeleton resulted in a red shift of the Q band and significantly modified the molecular-orbital electronic distributions just below the HOMO and just above the LUMO, with distortion of the typical Gouterman four-orbital arrangement of MOs. Two amphiphilic Ω-shaped ZnPcs (αPcS1 and αPcS2) bearing a π-conjugated side chain with an adsorption site at an α position of the Pc macrocycle were synthesized as sensitizers for dye-sensitized solar cells (DSSCs). The absorption spectra of αPcS1 and αPcS2 showed red shifted Q bands and a broad band from 350 to 550 nm assignable to the intramolecular charge-transfer transition from the ZnPc core to the side chains. Time-dependent DFT calculations provided a clear interpretation of the effect of the thiophene conjugation on the typical phthalocyanine core π MOs. Compound αPcS1 was used as a light-harvesting dye on a TiO2 electrode for a DSSC, which showed a panchromatic response in the range 400-800 nm with a power conversion efficiency of 5.5 % under one-sun conditions.

Aggregation Control of Robust Water-Soluble Zinc(II) Phthalocyanine-Based Photosensitizers.

A water-soluble zinc phthalocyanine (ZnPc) complex with four negatively charged electron-withdrawing sulfonic acid substituents at the nonperipheral positions (α-ZnTSPc) is found to have a high singlet oxygen (1O2) quantum yield and exhibits high photostability. The formation of aggregates is hindered and the highest occupied molecular orbital is significantly stabilized, making α-ZnTSPc potentially suitable for its use as a photosensitizer for photodynamic therapy and photoimmunotherapy. Atomic force microscopy (AFM) reveals that mixtures of the negatively charged α-ZnTSPc complex with a similar positively charged ZnPc were found to result in the self-assembly of one-dimensional accordion-like fibers. Supramolecular fibers can be formed in aqueous solutions through intermolecular electrostatic and donor-acceptor interactions between the two water-soluble ZnPcs.

An Alkyloxyphenyl Group as a Sterically Hindered Substituent on a Triphenylamine Donor Dye for Effective Recombination Inhibition in Dye-Sensitized Solar Cells.

Recombination reactions in dye-sensitized solar cells (DSSCs) may substantially decrease the open-circuit voltage (Voc) with cobalt complex redox electrolyte. Managing steric hindrance in the dye structure is necessary to inhibit recombination reactions and thereby increase the Voc and achieve high power-conversion efficiency (PCE). New dyes with large-sized donors based on triphenylamine and modified with 4-(hexyloxy)phenyl groups were developed to identify an effective inhibitor for the recombination reaction in DSSCs with a cobalt complex redox electrolyte. The 4-(hexyloxy)phenyl tetra-adducts dye MK-123 effectively inhibited the recombination reaction, and the DSSC fabricated using this dye exhibited the highest Voc (greater than 900 mV) among the cells with the investigated dyes. However, the short-circuit current (Jsc) of the MK-123 cell was lower than that of the cell with the simple triphenylamine donor dye, MK-89. In contrast, the cell with bis-adducts dye MK-136 also exhibited an increase in its Voc without a decrease in its Jsc. Among the investigated dyes, MK-136 exhibited the highest PCE of 8.9%. The effects of the steric hindrance of the 4-(hexyloxy)phenyl substituent are discussed.

Low-Symmetrical Zinc(II) Benzonaphthoporphyrazine Sensitizers for Light-Harvesting in Near-IR Region of Dye-Sensitized Solar Cells.

Two ring-expanded naphthalocyanine-based sensitizers NcS1 and NcS2 have been designed and synthesized to harvest near-IR light energy in dye-sensitized solar cells. Low-symmetrical "push-pull" structures of NcS1 and NcS2 enable the red-shift of absorption spectrum as well as the defined Q-band splitting. The zinc benzonaphthoporphyrazine sensitizer NcS1 possessing one carboxylic acid and six 2,6-diisopropylphenoxy units showed a PCE value of 3.2% when used as a light-harvesting dye on a TiO2 electrode under one sun condition. The NcS1 cell showed a broad photoresponse at wavelengths from 600 to 850 nm.

Structural effect of donor in organic dye on recombination in dye-sensitized solar cells with cobalt complex electrolyte.

The effect of the donor in an organic dye on the electron lifetime of dye-sensitized solar cells (DSSCs) employing a cobalt redox electrolyte was investigated. We synthesized organic dyes with donor moieties of carbazole, coumarin, triphenylamine, and N-phenyl-carbazole and measured the current-voltage characteristics and electron lifetimes of the DSSCs with these dyes. The cell with the triphenylamine donor dye produced the highest open circuit voltage and longest electron lifetime. On the other hand, the lowest open circuit voltage and shortest electron lifetime was obtained with coumarin donor dye, suggesting that the coumarin attracted the cobalt redox couples to the surface of the TiO2 layer, thus increasing the concentration of cobalt complex. On the other hand, the longest electron lifetime with triphenylamine was attributed to the blocking effect by steric hindrance of the nonplanar structure of the donor.

Deformation of redox-active polymer gel based on polysiloxane backbone and bis(benzodithiolyl)bithienyl scaffold.

Redox-active polymer gels consisting of polysiloxane backbone and bis(benzodithiolyl)bithienyl units have been designed and synthesized. The bis(benzodithiolyl)bithienyl units, which undergo interconversion between cyclic form and opened dicationic form, have been incorporated into polysiloxane backbone via hydrosilylation of vinyl-terminated bis(benzodithiolyl)bithienyl derivative and poly(methylhydrosiloxane) (PMHS) or poly(dimethylsiloxane-co-hydrogenmethylsiloxane) (PDMS-co-PMHS), resulting in polymer gels cross-linked with bis(benzodithiolyl)bithienyl units. After the incorporation of M1 into polysiloxane backbone, these polymer gels (P1 and P2) also exhibit redox responses associated with the electrochemical interconversion of the bis(benzodithiolyl)bithienyl moieties. The polymer gels show swelling behavior upon chemical oxidization, and bending behavior has been observed for the polymer gel immobilized poly(vinylidene difluoride) (PVdF) film. These results provide a useful perspective for fabricating redox-triggered polymer gel actuators based on the conformational change of the functional molecular unit.

Redox-driven molecular switches consisting of bis(benzodithiolyl)bithienyl scaffold and mesogenic moieties: synthesis and complexes with liquid crystalline polymer.

Molecular switches composed of a benzodithiolylbithienyl scaffold and biphenyl or terphenyl mesogenic substituents were designed and synthesized. The molecular switches could undergo redox-triggered interconversion between the cationic form and cyclized neutral form, and this was confirmed using cyclic voltammetry and UV-vis spectroscopy. Binary complexes consisting of the molecular switches and a liquid crystalline polymer (LCP) were prepared to investigate the function of these redox-active molecular switches as actuating dopants. X-ray diffraction measurements were performed to determine the differences between the layer spacings of the complexes in the liquid crystalline phase with the oxidized and reduced states of the molecular switches. The LCP that was doped with the oxidized cationic form of the molecular switch had layer spacings that were up to 4% larger than the layer spacings in the polymer that was doped with the reduced cyclized molecular switch. Our approach will allow stimulus-responsive deformable materials to be constructed and give an impetus for fabricating redox-driven soft actuators.

Improvement of TiO2/dye/electrolyte interface conditions by positional change of alkyl chains in modified panchromatic Ru complex dyes.

A series of panchromatic ruthenium sensitizers (MJ sensitizers) with attached thiophene and phenyl units bearing alkyl chains was synthesized. A new synthetic route was used to examine all possible positions for the alkyl chains. The absorption spectra showed the sum of a ruthenium complex and peripheral organic chromophore units. The hypochromic effect and blueshift of the metal-to-ligand charge-transfer band observed in the modified ruthenium sensitizers were suppressed by changing the positions of the alkyl chains on the attached thiophene ring. Changing only one alkyl chain also influenced the performance of dye-sensitized solar cells. Ruthenium sensitizer MJ-10 with bulky substituent harvests visible and near-infrared light, and solar cells sensitized by MJ-10 exhibit an efficiency of 9.1% under 1 sun irradiation.

Molecular design rule of phthalocyanine dyes for highly efficient near-IR performance in dye-sensitized solar cells.

A series of zinc-phthalocyanine sensitizers (PcS16-18) with different adsorption sites have been designed and synthesized in order to investigate the dependence of adsorption-site structures on the solar-cell performances in zinc-phthalocyanine based dye-sensitized solar cells. The change of adsorption site affected the electron injection efficiency from the photoexcited dye into the nanocrystalline TiO2 semiconductor, as monitored by picosecond time-resolved fluorescence spectroscopy. The zinc-phthalocyanine sensitizer PcS18, possessing one carboxylic acid directly attached to the ZnPc ring and six 2,6-diisopropylphenoxy units, showed a record power conversion efficiency value of 5.9 % when used as a light-harvesting dye on a TiO2 electrode under one simulated solar condition.

Washable PEDOT:PSS Coated Polyester with Submicron Sized Fibers for Wearable Technologies.

The use of non-metallic conductive yarns in wearable technologies like smart textiles requires compliant washable fibers that can withstand domestic washing without losing their conductive properties. A one-pot coating with PEDOT:PSS conductive polymers was applied to polyester submicron fibers, increasing the water resistance and washability under various domestic washing conditions. Plasma treatment of the untreated samples improved the anchoring of the coating to the fibers, producing smooth and homogeneous coatings. The primary doping of PEDOT:PSS with ethylene glycol (EG), dimethyl sulfoxide (DMSO), and a non-ionic surfactant as well as the secondary doping of the composite fibers improved the sheet resistance at room temperature. The as-obtained composite materials showed similar mechanical properties as the parent fibers, indicating that the coating and post-treatment do not affect the overall mechanical property of the composite. The performance of the composites under different temperature and humidity conditions and washability using the standardized ISO 6330:2012 procedure for domestic washing and drying showed that the obtained composites are good candidates for reliable washable wearable technologies, such as all-organic washable Joule heaters in functional textiles.

Nanofiltration Performance of Poly(p-xylylene) Nanofilms with Imidazole Side Chains.

Herein, we report the nanofiltration performance of poly(p-xylylene) thin films with imidazole side chains that were deposited onto commercial polyethersulfone ultrafiltration membranes using a chemical vapor deposition process. The resulting thin films with a few tens of nanometers exhibited water permeation under a pressure difference of 0.5 MPa and selectively rejected water-soluble organic dyes based on their molecular sizes. Additionally, thin flaky ZIF-L crystals (Zn(mim)2·(Hmim)1/2·(H2O)3/2) (Hmim = 2-methylimidazole) formed on the surface of imidazole-containing poly(p-xylylene) films, and the composite films demonstrated the ability to adsorb methylene blue molecules within the cavities of ZIF-L.

Neuromorphic System Using Memcapacitors and Autonomous Local Learning.

Artificial intelligence is used for various applications and is promising as an indispensable infrastructure in future societies. Neural networks are representative technologies that imitate human brains and exhibit various advantages. However, the size is bulky, the power is huge, and some advantages are not demonstrated because they are executed on Neumann-type computers. Neuromorphic systems are biomimetic systems from the hardware level to implement neuron and synapse elements, and the size is compact, the power is low, and the operation is robust. However, because the conventional ones are not composed of fully optimized hardware, the power is not yet minimal, and extra control circuits must be used. In this article, we developed a neuromorphic system using memcapacitors and autonomous local learning. By using memcapacitors, the power can be minimal, and by using autonomous local learning, the control circuits to handle the synapse elements can be deleted. First, the memcapacitors are completed in a cross-bar array, where the ferroelectric layers are sandwiched between the horizontal and perpendicular electrodes. The polarization and capacitance exhibit hysteresis due to the dielectric polarization. Next, autonomous local learning is introduced as follows. During the training phase, associative patterns to be memorized are directly sent, relatively high voltages are applied, and dielectric polarizations are induced. During the operation phase, relatively low voltages are applied, and input signals are weighted with the capacitances of the memcapacitors, summed, and transferred as the output signals. Finally, the experimental system is set up, and the experimental results are acquired. The memorized patterns during the training phase, distorted patterns as the input signals during the operation phase, and retrieved patterns as the output signals in the operation phase are shown. Researchers found that the retrieved patterns are completely the same as the memorized patterns. This means that the neuromorphic system works as an associative memory.

High-k Solution-Processed Barium Titanate/Polysiloxane Nanocomposite for Low-Temperature Ferroelectric Thin-Film Transistors.

Ferroelectric nanoparticles have attracted much attention for numerous electronic applications owing to their nanoscale structure and size-dependent behavior. Barium titanate (BTO) nanoparticles with two different sizes (20 and 100 nm) were synthesized and mixed with a polysiloxane (PSX) polymer forming a nanocomposite solution for high-k nanodielectric films. Transition from the ferroelectric to paraelectric phase of BTO with different nanoparticle dimensions was evaluated through variable-temperature X-ray diffraction measurement accompanied by electrical analysis using capacitor structures. A symmetric single 200 peak was constantly detected at different measurement temperatures for the 20 nm BTO sample, marking a stable cubic crystal structure. 100 nm BTO on the other hand shows splitting of 200/002 peaks correlating to a tetragonal crystal form which further merged, thus forming a single 200 peak at higher temperatures. Smaller BTO dimension exhibits clockwise hysteresis in capacitance-voltage measurement and correlates to a cubic crystal structure which possesses paraelectric properties. Bigger BTO dimension in contrast, demonstrates counterclockwise hysteresis owing to their tetragonal crystal form. Through further Rietveld refinement analysis, we found that the tetragonality (c/a) of 100 nm BTO decreases at a higher temperature which narrows the hysteresis window. A wider hysteresis window was observed when utilizing 100 nm BTO compared to 20 nm BTO even at a lower loading ratio. The present findings imply different hysteresis mechanisms for BTO nanoparticles with varying dimensions which is crucial in understanding the role of how the BTO size tunes the crystal structures for integration in thin-film transistor devices.

Flexible tactile sensor using the reversible deformation of poly(3-hexylthiophene) nanofiber assemblies.

In this letter, we report a simple approach to fabricating scalable flexible tactile sensors using a nanofiber assembly of regioregular poly(3-hexylthiophene) (P3HT). Uniform P3HT nanofibers are obtained through a continuous electrospinning process using a homogeneous solution of high-molecular-weight P3HT. The P3HT nanofibers are oriented by collecting them on a rotating drum collector. Small physical inputs into the self-standing P3HT nanofiber assemblies give rise to additional contact among neighboring nanofibers, which results in decreased contact resistance in directions orthogonal to the nanofiber orientation. The P3HT nanofiber assemblies could detect pressure changes and bending angles by monitoring the resistance changes, and the sensor responses were repeatable.