Solid‐state dye‐sensitized and bulk heterojunction solar cells using TiO2 and ZnO nanostructures: recent progress and new concepts at the borderline

In the field of photovoltaic energy conversion, hybrid inorganic/organic devices represent promising alternatives to standard photovoltaic systems in terms of exploiting the specific features of both organic semiconductors and inorganic nanomaterials. Two main categories of hybrid solar cells coexist today, both of which make much use of metal oxide nanostructures based on titanium dioxide (TiO₂) and zinc oxide (ZnO) as electron transporters. These metal oxides are cheap to synthesise, are non‐toxic, are biocompatible and have suitable charge transport properties, all these features being necessary to demonstrate highly efficient solar cells at low cost. Historically, the first hybrid approach developed was the dye‐sensitized solar cell (DSSC) concept based on a nanostructured porous metal oxide electrode sensitized by a molecular dye. In particular, solid‐state hybrid DSSCs, which reduce the complexity of cell assembly, demonstrate very promising performance today. The second hybrid approach exploits the bulk heterojunction (BHJ) concept, where conjugated polymer/metal oxide interfaces are used to generate photocurrent. In this context, we review the recent progress and new concepts in the field of hybrid solid‐state DSSC and BHJ solar cells based on TiO₂ and ZnO nanostructures, incorporating dyes and conjugated polymers. We point out the specificities in common hybrid device structures and give an overview on new concepts, which couple and exploit the main advantages of both DSSC and BHJ approaches. In particular, we show that there is a trend of convergence between both DSSC and BHJ approaches into mixed concepts at the borderline which may allow in the near future the development of hybrid devices for competitive photovoltaic energy conversion. Copyright © 2011 Society of Chemical Industry     

Cold sintering and co‐firing of a multilayer device with thermoelectric materials

Cold‐sintered ZnO and Ca₃Co₄O₉ polycrystalline materials were shown to have thermoelectric properties comparable to those of conventionally sintered ceramics. Extending these processing conditions into a cold sintering co‐fired ceramic (CSCC) technology, we integrated n‐type and p‐type thermoelectric oxides and a separating insulating layer to demonstrate functional multilayer thermoelectric generator devices. A co‐fired structure with an insulating 8 mol% yttria‐stabilized zirconia (8YSZ) layer enabled multilayer thermoelectric generators (TEG) to be fabricated with a 5 n‐p junction device (20 layers). A transmission electron microscopy analysis of the interfaces between the various materials under the co‐firing cold sintering showed some interdiffusion of chemical constitutes in a 2.0 μm interface region between the respective ceramic phases. The co‐firing of multilayer ceramic and polymer structures were also shown to be possible using insulation layers of polytetrafluoroethylene (PTFE) thermoplastic layers. This demonstrated the feasibility of a single‐step process for new structures with both ceramics and polymers, opening up new directions for many new device designs.     

Enhancement in thermoelectric properties using a P‐type and N‐type thin‐film device structure

In this study, we have fabricated thermoelectric devices with p‐type and n‐type conducting polymers and research the effect of device structure with the thermoelectric properties. It was found that the p‐type and n‐type structure greatly enhances the device's electrical conductivity due to separated charge carrier channels, but the Seebeck coefficient was reduced due to the increase of charge density by doping. Photoexcitation can improve the device's thermoelectric properties and can increase the Seebeck coefficient and electrical conductivity with increasing doping concentration simultaneously. The increases in both properties are due to the phonon–electron coupling effect: the concentration of electrons and holes are increased under illumination, and the phonon component of the heat flux can be reduced by phonon scattering. Consequently, the thermoelectric device structure can improve the efficiency of thermoelectric conversion. The P3HT:PCBM devices demonstrate a significant enhancement in the power factor (PF = S²σ), with a maximum value of ZT = 0.5 at 147°C, in which the PF value (34.8 μV/cm K²) is bigger than Bi₂Te₃/Sb₂Te₃ superlattice devices at room temperature. POLYM. COMPOS., 34:1728–1734, 2013. © 2013 Society of Plastics Engineers     

PMMA composites of single‐walled carbon nanotubes‐graft‐PMMA

To facilitate the dispersion of single‐walled carbon nanotubes (SWCNT) into poly(methyl methacrylate) (PMMA), SWCNT were functionalized with a RAFT chain transfer agent, and PMMA was grafted from the SWCNT by reversible addition–fragmentation transfer (RAFT) polymerization to give SWCNT‐g‐PMMA containing 6 wt % PMMA. SWCNT‐g‐PMMA in the form of small bundles was dispersed into PMMA matrices. The SWCNT‐g‐PMMA filler increased the glass transition temperature (T_g) of the composite when the matrix molecular weight M_n was less than the graft molecular weight, but not when the matrix M_n was equal to or greater than the graft M_n. The threshold of electrical conductivity of the composites as a function of weight percent SWCNT increased from 0.2% when matrix M_n was less than graft M_n to about 1% when matrix M_n was greater than graft M_n. Dynamic mechanical analyses of the composites having graft M_n less than or equal to matrix M_n showed broader rubbery plateaus with increased SWCNT content but no significant differences between samples with different grafted PMMAs. The results indicate that lower M_n matrix wets the SWCNT‐g‐PMMA whereas higher M_n matrix does not wet the SWCNT‐g‐PMMA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39884.     

Enantioenriched Calcium‐(R)‐5,5′,6,6′,7,7′,8,8′‐Octahydro‐BINOL (H8‐BINOL): An Efficient Catalyst for the Creation of a Quaternary Stereocenter#

An efficient catalyst for the creation of a quaternary stereocenter has been developed utilizing easily available, eco‐friendly CaCl₂ and applied for enantioselective carbon‐carbon bond forming reactions. Among the surveyed ligands, it was found that (R)‐5,5′,6,6′,7,7′,8,8′‐octahydro‐BINOL‐Ca ( 2f ) gave maximum ee (72%) with excellent yields.     

Polystyrene composites of single‐walled carbon nanotubes‐graft‐polystyrene

Single‐walled carbon nanotubes (SWCNTs) dispersed in N‐methylpyrrolidone (NMP) were functionalized by addition of polystyryl radicals from 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐ended polystyrene (SWCNT‐g‐PS). The amount of polystyrene grafted to the nanotubes was in the range 20‐25 wt% irrespective of polystyrene number‐average molecular weight ranging from 2270 to 49 500 g mol^?1. In Raman spectra the ratios of D‐band to G‐band intensity were similar for all of the polystyrene‐grafted samples and for the starting SWCNTs. Numerous near‐infrared electronic transitions of the SWCNTs were retained after polymer grafting. Transmission electron microscopy images showed bundles of SWCNT‐g‐PS of various diameters with some of the polystyrene clumped on the bundle surfaces. Composites of SWCNT‐g‐PS in a commercial‐grade polystyrene were prepared by precipitation of mixtures of the components from NMP into water, i.e. the coagulation method of preparation. Electrical conductivities of the composites were about 10^?15 S cm^?1 and showed no percolation threshold with increasing SWCNT content. The glass transition temperature (T_g) of the composites increased at low filler loadings and remained constant with further nanotube addition irrespective of the length and number of grafted polystyrene chains. The change of heat capacity (ΔC_p) at T_g decreased with increasing amount of SWCNT‐g‐PS of 2850 g mol^?1, but ΔC_p changed very little with the amount of SWCNT‐g‐PS of higher molecular weight. The expected monotonic decrease in ΔC_p coupled with the plateau behavior of T_g suggests there is a limit to the amount that T_g of the matrix polymer can increase with increasing amount of nanotube filler. Copyright © 2012 Society of Chemical Industry     

Predicted Ligands for the Human Urotensin‐II G Protein‐Coupled Receptor with Some Experimental Validation

Human Urotensin‐II (U‐II) is the most potent mammalian vasoconstrictor known. 1 Thus, a U‐II antagonist would be of therapeutic value in a number of cardiovascular disorders. 2 Here, we describe our work on the prediction of the structure of the human U‐II receptor (hUT₂R) using GEnSeMBLE (GPCR Ensemble of Structures in Membrane BiLayer Environment) complete sampling Monte Carlo method. With the validation of our predicted structures, we designed a series of new potential antagonists predicted to bind more strongly than known ligands. Next, we carried out R‐group screening to suggest a new ligand predicted to bind with 7 kcal mol^?1 better energy than 1‐{2‐[4‐(2‐bromobenzyl)‐4‐hydroxypiperidin‐1‐yl]ethyl}‐3‐(thieno[3,2‐b]pyridin‐7‐yl)urea, the designed antagonist predicted to have the highest affinity for the receptor. Some of these predictions were tested experimentally, validating the computational results. Using the pharmacophore generated from the predicted structure for hUT₂R bound to ACT‐058362, we carried out virtual screening based on this binding site. The most potent hit compounds identified contained 2‐(phenoxymethyl)‐1,3,4‐thiadiazole core, with the best derivative exhibiting an IC₅₀ value of 0.581 μM against hUT₂R when tested in vitro. Our efforts identified a new scaffold as a potential new lead structure for the development of novel hUT₂R antagonists, and the computational methods used could find more general applicability to other GPCRs.     

Combined soft lithographic transfer‐printing and patterning method of highly fluorinated polymers as a facile surface treatment protocol

A combined soft lithographic transfer‐printing and patterning method of highly fluorinated polymers was investigated aiming to establish a facile surface treatment protocol for various substrates. Spin‐coated layers of poly(1H,1H,2H,2H‐perfluorodecyl methacrylate) (PFDMA) on patterned polydimethylsiloxane (PDMS) molds were transfer‐printed successfully on silicon, glass, aluminum substrates, resulting in the well‐controlled production of nano to micrometer‐scale periodic structures. With careful optimization of the dimension and density of the PFDMA patterns, it was possible to achieve a water contact angle as high as 175° on the transfer‐printed highly fluorinated polymer film. One of the advantages of the transfer‐patterning method is that highly fluorinated polymer films can be printed on curved surfaces while retaining their superhydrophobic and corrosion‐prevention character. In addition, the transfer‐printed PFDMA layers on the glass plates showed enhanced light transmission, which led to the extraction of 10% more light when they were applied to the emitting side of green organic light‐emitting devices. The micro‐patterned PFDMA surfaces also exhibited a significantly reduced level of bacterial adhesion when they were incubated in human bile juice. These results strongly suggest that the proposed facile transfer‐patterning protocol of highly fluorinated polymer films can be a suitable surface‐treatment technique for implantable electronic devices that exhibit improved device performance and anti‐biofouling nature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45184.     

Dual‐type electrochromic device with single wall carbon nano tube employment in gel electrolyte

A novel conducting polymer‐based electrochromic device is proposed with single walled carbon nanotube (SWCNT) employment in gel electrolyte. Electrochemical film deposition on indium tin oxide substrates were governed and monitored via cyclic‐voltametry. Construction details of the proposed device are presented with its optimized parameters and SWCNT doping caused a noteworthy enhancement in efficiency and stability of the device performance. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Synthesis of High‐Performance Pebax®‐1074/DD3R Mixed‐Matrix Membranes for CO2/CH4 Separation

This work deals with the incorporation of deca‐dodecasil 3 rhombohedral (DD3R) zeolite as an inorganic filler into the Pebax®‐1074‐based polymer matrix to enhance the performance of the pure polymeric membrane in CO₂/CH₄ separation. The membranes were fabricated with different concentrations of DD3R. Separation performances of the membranes were investigated at various feed pressures and temperatures. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC) analysis of the prepared membranes were performed. In the best case, selectivity for CO₂/CH₄ separation was improved, while the permeability decreased. Membranes with 1 and 5 wt % DD3R were located in the acceptable region beyond the Robeson plot (1991) for CO₂/CH₄ gas pairs.     

Miscibility Determination from Gas‐Oil Interfacial Tension and P‐R Equation of State

Recently a new experimental technique of vanishing interfacial tension (VIT) has been developed to enable rapid and cost‐effective determination of miscibility in gas‐oil systems. In this study, VIT experiments have been extended to two standard gas‐oil systems of n‐decane‐CO₂ and live decane‐CO₂ at elevated pressures and temperatures. The VIT miscibilities of the two standard gas‐oil systems and the two reservoir crude oil‐gas systems, namely Rainbow Keg River (RKR) and Terra Nova, were compared with Peng‐Robinson (P‐R) equation of state (EOS) calculations. The close match of VIT miscibilities with other conventional experimental techniques in the standard gas‐oil systems, as well as the reasonable match obtained with untuned PR‐EOS calculations for several systems studied, clearly demonstrates the sound conceptual basis of VIT technique to determine fluid‐fluid miscibility in multi‐component hydrocarbon systems.     

(R)‐α‐Lipoyl‐Glycyl‐L‐Prolyl‐L‐Glutamyl Dimethyl Ester Codrug as a Multifunctional Agent with Potential Neuroprotective Activities

The (R)‐α‐lipoyl‐glycyl‐L ‐prolyl‐L ‐glutamyl dimethyl ester codrug (LA‐GPE, 1 ) was synthesized as a new multifunctional drug candidate with antioxidant and neuroprotective properties for the treatment of neurodegenerative diseases. Physicochemical properties, chemical and enzymatic stabilities were evaluated, along with the capacity of LA‐GPE to penetrate the blood–brain barrier (BBB) according to an in vitro parallel artificial membrane permeability assay for the BBB. We also investigated the potential effectiveness of LA‐GPE against the cytotoxicity induced by 6‐hydroxydopamine (6‐OHDA) and H₂O₂ on the human neuroblastoma cell line SH‐SY5Y by using the 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) reduction assay. Our results show that codrug 1 is stable at both pH 1.3 and 7.4, exhibits good lipophilicity (log P=1.51) and a pH‐dependent permeability profile. Furthermore, LA‐GPE was demonstrated to be significantly neuroprotective and to act as an antioxidant against H₂O₂‐ and 6‐OHDA‐induced neurotoxicity in SH‐SY5Y cells.     

Synthesis and light‐emitting properties of a novel π‐conjugated poly[di(p‐phenyleneethynylene)‐alt‐ (p‐phenylenecyanovinylene)] containing n‐octyloxy side branches

A novel π‐conjugated poly[di(p‐phenyleneethynylene)‐alt‐(p‐phenylenecyanovinylene)] having n‐octyloxy side chains (PPE‐C₈PPE‐PPV) was prepared by polymerization of the monomer DEDB with BCN. Chemical structure of the polymer obtained was confirmed by ¹H NMR, FTIR, and EA. PPE‐C₈PPE‐PPV had a molecular weight enough to fabricate the electroluminescent (EL) device, and showed a good organosolubility, excellent thermal stability, and film‐forming property. In UV absorption and PL spectra in film it showed a maximum at 430 and 543 nm, respectively, which appeared 5 and 41 nm longer wavelengths than that of the solution, respectively. HOMO, LUMO energy levels and band gap were determined to be ?5.70, ?3.29, and 2.41 eV, respectively. Two EL devices with low‐work function cathodes were fabricated with the structures of ITO/PEDOT/PPE‐C₈PPE‐PPV/cathodes (LiF/Al and Mg:Ag/Ag). The both devices exhibited a bright green light emission at 545 nm and the maximum luminescence of 197 cd/cm² (LiF/Al) and 158 cd/cm² (Mg:Ag/Ag). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

X9R BaTiO3‐Based Dielectric Ceramics with Multilayer Core–Shell Structure Produced by Polymer‐Network Gel Coating Method

The modified polymer‐network gel route has been developed to prepare a multilayer core –shell structure of BaTiO ₃‐ based dielectric ceramics. The core of particle was BaTiO₃, whereas 0.7BaTiO₃–0.3Bi(Zn_1/2Ti_1/2)O₃ (0.7BT–0.3BZT) and Nb oxides were coated as the multilayer shell compositions, which were confirmed by energy dispersive spectroscopy testing. The dielectric properties of BaTiO₃‐based samples with multilayer core–shell structure were found to meet the X9R specification. The dielectric constant was 1190 and the dielectric loss was 1.3% at room temperature.     

Synthesis and device performance of an oxygen‐interrupted bipolar polymer host with carbazole and triphenylphosphine oxide in the main chain

A novel bipolar polymer host PC10CzPO, carrying hole‐transporting carbazole and electron‐transporting triphenylphosphine oxide units in the oxygen‐interrupted main chain, was synthesized and characterized. In addition to its excellent thermal stability and miscibility with phosphors, PC10CzPO is also reported to have a triplet energy (E_T) as high as 2.83 eV due to oxygen‐interrupted π‐conjugation, ensuring that PC10CzPO can be used as a suitable host material. The PC10CzPO‐based phosphorescent devices were investigated and compared, while doping with typical blue phosphor {iridium(III)[bis(4,6‐difluorophenyl)pyridinato‐N, C2]picolinate, FIrpic)}, green phosphor {tris[2‐(p‐tolyl)pyridine]iridium(III), Ir(mppy)₃}, and red phosphor [bis(1‐phenyl‐isoquinoline‐C2,N)(acetylacetonato)iridium(III), Ir(piq)₂acac]. As a result, the FIrpic‐based blue devices showed better device performances than those of red and green devices, which was ascribed to more effective energy transfer. This indicates that the choice of proper host and dopant emitters to fabricate phosphorescent polymer light emitting diodes (PhPLED) is a simple and effective approach to optimize device performances. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44461.     

Structural evolution of the R‐T phase boundary in KNN‐based ceramics

Although a rhombohedral‐tetragonal (R‐T) phase boundary is known to substantially enhance the piezoelectric properties of potassium‐sodium niobate ceramics, the structural evolution of the R‐T phase boundary itself is still unclear. In this work, the structural evolution of R‐T phase boundary from ?150°C to 200°C is investigated in (0.99?x)K_0.5Na_0.5Nb_1?ySb_yO₃–0.01CaSnO₃–xBi_0.5K_0.5HfO₃ (where x = 0‐0.05 with y = 0.035, and y = 0‐0.07 with x = 0.03) ceramics. Through temperature‐dependent powder X‐ray diffraction (XRD) patterns and Raman spectra, the structural evolution was determined to be Rhombohedral (R, <?125°C)→Rhombohedral + Orthorhombic (R + O, ?125°C to 0°C)→Rhombohedral + Tetragonal (R + T, 0 °C to 150°C)→dominating Tetragonal (T, 200°C to Curie temperature (T_C)) → Cubic (C, >T_C). In addition, the enhanced electrical properties (e.g., a direct piezoelectric coefficient (d₃₃) of ~450 ± 5 pC/N, a conversion piezoelectric coefficient () of ~580 ± 5 pm/V, an electromechanical coupling factor (k_p) of ~0.50 ± 0.02, and T_C~250°C), fatigue‐free behavior, and good thermal stability were exhibited by the ceramics possessing the R‐T phase boundary. This work improves understanding of the physical mechanism behind the R‐T phase boundary in KNN‐based ceramics and is an important step toward their adoption in practical applications.     

Greatly enhanced photocurrent in inorganic perovskite [KNbO3]0.9[BaNi0.5Nb0.5O3‐σ]0.1 ferroelectric thin‐film solar cell

Inorganic perovskite [KNbO₃]_0.9[BaNi_0.5Nb_0.5O_3‐σ]_0.1 (KBNNO) ferroelectric thin films with narrow band gap (1.83 eV) and high room‐temperature remnant polarization (Pr = 0.54 μC/cm²) was grown successfully on the Pt(111)/Ti/SiO₂/Si(100) substrates by pulsed laser deposition. Ferroelectric solar cells with a basic structure of ITO/KBNNO/Pt were further prepared based on these thin films, which exhibited obvious external‐poling dependent photovoltaic effects. When the devices were negatively poled, the short‐circuit current and open‐circuit voltage were both significantly higher than those of the devices poled positively. This is attributed to enhanced charge separation under the depolarization field induced by the negative poling, which is superimposed with the built‐in field induced by the Schottky barriers at the interfaces between KBNNO and the two electrodes. When a poling voltage of ‐1 V was applied, the device showed a short‐circuit current as high as 27.3 μA/cm², which was by two orders of magnitude larger than that of the KBNNO thick‐film (20 μm) devices reported previously. This work may inspire further exploration for lead‐free inorganic perovskite ferroelectric photovoltaic devices.     

Synthesis and light‐emitting properties of new poly(p‐phenylenevinylene) derivatives containing oxadiazole moiety

Two new poly(p‐phenylenevinylene) (PPV) derivatives containing the oxadiazole moiety (OXA–PPV1 and OXA–PPV2) were synthesized by the Wittig condensation polymerization reaction and their thermal and light‐emitting properties were investigated. The single‐layer and triple‐layer electroluminescent (EL) devices with configurations of ITO/OXA–PPV1/Al and ITO/OXA–PPV1/OXD/Alq₃/Al were fabricated. They both exhibited blue emission at 460 nm. For comparison, the PPV derivative containing the oxadiazole moiety only in the side chains (OXA–PPV2) was also synthesized. Both single‐layer and triple‐layer EL devices with OXA–PPV2 as the emissive layer emitted green‐light at 560 nm. The turn‐on voltages of the triple‐layer device was 11 V for OXA–PPV1 and 8 V for OXA–PPV2. The triple‐layer EL devices showed much better performance than that of the single‐layer devices. The spectra indicated that energy or electron transfer occurred from the side‐chain oxadiazole to the main‐chain styrene unit. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2424–2428, 2002     

Determination of kinetics of CO2 absorption in solutions of 2‐amino‐2‐methyl‐1‐propanol using a microfluidic technique

The kinetics for the reactions of carbon dioxide with 2‐amine‐2‐methyl‐1‐propanol (AMP) and carbon dioxide (CO₂) in both aqueous and nonaqueous solutions were measured using a microfluidic method at a temperature range of 298–318 K. The mixtures of AMP‐water and AMP‐ethylene glycol were applied for the working systems. Gas‐liquid bubbly microflows were formed through a microsieve device and used to determine the reaction characteristics by online observation of the volume change of microbubbles at the initial flow stage. In this condition, a mathematical model according to zwitterion mechanism has been developed to predict the reaction kinetics. The predicted kinetics of CO₂ absorption in the AMP aqueous solution verified the reliability of the method by comparing with literatures’ results. Furthermore, the reaction rate parameters for the reaction of CO₂ with AMP in both solutions were determined. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4358–4366, 2015     

Increase in flame retardance of glass‐epoxy laminates without halogen or phosphorous compounds by simultaneous use of incombustible‐gas generator and charring promoter

Highly flame‐resistant glass‐epoxy laminates without flame‐retarding additives such as halogen and phosphorous compounds have been developed to overcome environmental problems caused by these additives. The laminates consist mainly of a self‐extinguishing epoxy‐resin compound (phenol aralkyl), an incombustible‐gas generator (amino‐triazine‐novolac hardener: ATN hardener), and inorganic materials such as a charring promoter (zinc molybdate on talc: ZMT) and a limited amount of harmless metal hydroxide (aluminum trihydroxide: ATH). They are highly flame‐resistant and have other beneficial characteristics, including soldering‐heat resistance, humidity resistance, electronic properties, and processing advantages. These qualities make them applicable enough to replace the FR‐4 type printed wiring boards (PWBs) that are widely used today. Simultaneously using the ATN hardener and ZMT in the laminates, including the epoxy‐resin compound and ATH, greatly improved their flame retardance. We then reduced the amount of ATH to obtain even better flame retardance in the laminates. This reduction of the ATH, consequently, improved other practical characteristics such as soldering‐heat resistance, humidity resistance, and electronic properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3367–3375, 2006