A novel natural scaffold layer improving efficiency, stability and reproducibility of Perovskite solar cells.

In this study, our hypothesis was to demonstrate the usability of a natural clay structure as scaffold layer in perovskite solar cells (PSCs). Sepiolite, which is a natural and environmentally friendly clay structure, has a very high active surface area and can easily be dispersed in solvents. In addition we predicted that crystallization could easily occur on their surfaces due to their surface chemistry. In the study, we firstly used a natural clay as scaffold layer in PSCs. It is observed that, efficiency, reproducibility and stability of PSCs have been significantly improved. Improvements in efficiency have been observed to be between 30 and 50% depending on the type of perovskite solvent used. In addition, the surface chemistry of the sepiolite resulted in better crystallization as well as stability. Due to its high-water adsorption capability, sepiolite makes the perovskite crystal more stable by trapping the residual water molecules as well as penetrated water molecules from environment. Consequently, we demonstrated that, a natural, low-cost and environmentally friendly clay may be an alternative material which may contribute to the commercialization of PSCs.

Amplifying the dielectric constant of shellac by incorporating natural clays for organic field effect transistors (OFETs).

We demonstrate in this work the practical use of uniform mixtures of a bioresin shellac and four natural clays, i.e. montmorillonite, sepiolite, halloysite and vermiculate as dielectrics in organic field effect transistors (OFETs). We present a thorough characterization of their processability and film forming characteristic, surface characterization, elaborate dielectric investigation and the fabrication of field effect transistors with two classic organic semiconductors, i.e. pentacene and fullerene C60. We show that low operating voltage of approximately 4 V is possible for all the OFETs using several combinations of clays and shellac. The capacitance measurements show an improvement of the dielectric constant of shellac by a factor of 2, to values in excess of 7 in the uniform mixtures of sepiolite and montmorillonite with this bioresin.

Development of Highly Luminescent Water-Insoluble Carbon Dots by Using Calix[4]pyrrole as the Carbon Precursor and Their Potential Application in Organic Solar Cells.

Carbon dots (CDs) are carbon-based fluorescent nanomaterials that are of interest in different research areas due to their low cost production and low toxicity. Considering their unique photophysical properties, hydrophobic/amphiphilic CDs are powerful alternatives to metal-based quantum dots in LED and photovoltaic cell designs. On the other hand, CDs possess a considerably high amount of surface defects that give rise to two significant drawbacks: (1) causing decrease in quantum yield (QY), a crucial drawback that limits their utilization in LEDs, and (2) affecting the efficiency of charge transfer, a significant factor that limits the use of CDs in photovoltaic cells. In this study, we synthesized highly luminescent, water-insoluble, slightly amphiphilic CDs by using a macrocyclic compound, calix[4]pyrrole, for the first time in the literature. Calix[4]pyrrole-derived CDs (CP-DOTs) were highly luminescent with a QY of over 60% and size of around 4-10 nm with graphitic structure. The high quantum yield of CP-DOTs indicated that they had less amount of surface defects. Furthermore, CP-DOTs were used as an additive in the active layer of organic solar cells (OSC). The photovoltaic parameters of OSCs improved upon addition of CDs. Our results indicated that calix[4]pyrrole is an excellent carbon precursor to synthesize highly luminescent and water-insoluble carbon dots, and CDs derived from calix[4]pyrrole are excellent candidates to improve optoelectronic devices.

Rubrene single crystal solar cells and the effect of crystallinity on interfacial recombination.

Single crystal studies provide a better understanding of the basic properties of organic photovoltaic devices. Therefore, in this work, rubrene single crystals with a thickness of 250 nm to 1000 nm were used to produce an inverted bilayer organic solar cell. Subsequently, polycrystalline rubrene (orthorhombic, triclinic) and amorphous bilayer solar cells of the same thickness as single crystals were studied to make comparisons across platforms. To investigate how single crystal, polycrystalline (triclinic-orthorhombic) and amorphous forms alter the charge carrier recombination mechanism at the rubrene/PCBM interface, light intensity measurements were carried out. The light intensity dependency of the JSC, VOC and FF parameters in organic solar cells with different forms of rubrene was determined. Monomolecular (Shockley Read Hall) recombination is observed in devices employing amorphous and polycrystalline rubrene in addition to bimolecular recombination, whereas the single crystal device is weakly affected by trap assisted SRH recombination due to reduced trap states at the donor acceptor interface. To date, the proposed work is the only systematic study examining transport and interface recombination mechanisms in organic solar cells produced by different structure forms of rubrene.

Improved visible light-driven photocatalytic degradation of methylene blue and methyl red by boron-doped carbon quantum dots.

The synthesis of fluorescent carbon quantum dots (CQDs) and their applications have attracted great attention due to their excellent properties. Especially, the unique visible-light absorption and photo-induced electron transfer properties make CQDs available in photocatalytic degradation of organic dye pollutants in water resources. Herein, we synthesized nondoped CQDs and boron-doped CQDs (B-CQDs) by hydrothermal method and compared their photocatalytic degradation activity of methylene blue (MB) and methyl red (MR) dyes under visible light irradiation. The characterization outcomes showed that the optical and structural properties can be easily improved by doping with hetero-atom, thereby photocatalytic performance. As expected, the photodegradation performance of both organic dyes in model solutions by B-CQDs was higher than that of CQDs. MB and MR dyes were photodegraded over 95% by B-CQDs in 90 and 120 min visible light irradiation, respectively. Eventually, the results revealed that nondoped CQDs and B-CQDs are excellent candidates for the degradation of organic dyes because of their high photocatalytic performance under visible light illumination.

Inhibition Effects of Different Toothpastes on Demineralisation of Incipient Enamel Lesions.

PURPOSE: To evaluate the inhibitory effects of different toothpastes on demineralisation of incipient enamel lesions using a toothbrush simulator. MATERIALS AND METHODS: Fifty enamel specimens were prepared from extracted human molars. The specimens were randomly assigned to the following groups (n = 10/group): 1. no treatment (control); 2. toothpaste containing arginine (ProRelief, Colgate;); 3. fluoride toothpaste (Pronamel, Sensodyne GlaxoSmithKlein); 4. tooth mousse containing casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) (Recaldent, GC); 5. toothpaste (Restore, Dr. Collins) containing bioactive glass (NovaMin, GlaxoSmithKlein). All specimens were exposed to pH cycling. The remineralising agents were applied to the samples with a toothbrush simulator for 2 min twice a day for five days. The weight percentage of mineral changes for the elements calcium (Ca), phosphorus (P), sodium (Na) and silica (Si) were measured by SEM energy-dispersive x-ray spectroscopy (SEM-EDX). SEM revealed properties of treated enamel surfaces. The data were analysed using one-way ANOVA. RESULTS: Statistically significantly higher levels of Ca and P were found in all groups compared to the control (p < 0.05). CONCLUSIONS: The toothpastes' efficacy of inhibiting demineralisation depended on the active ingredients in the respective toothpaste. The demineralisation inhibition efficacy of the tested toothpastes depended on the active ingredients in the toothpaste.

Enhanced Device Efficiency and Long-Term Stability via Boronic Acid-Based Self-Assembled Monolayer Modification of Indium Tin Oxide in a Planar Perovskite Solar Cell.

Interfacial engineering is essential for the development of highly efficient and stable solar cells through minimizing energetic losses at interfaces. Self-assembled monolayers (SAMs) have been shown as a handle to tune the work function (WF) of indium tin oxide (ITO), improving photovoltaic cell performance and device stability. In this study, we utilize a new class of boronic acid-based fluorine-terminated SAMs to modify ITO surfaces in planar perovskite solar cells. The SAM treatment demonstrates an increase of the WF of ITO, an enhancement of the short-circuit current, and a passivation of trap states at the ITO/[poly(3,4ethylenedioxylenethiophene):poly(styrenesulfonic acid)] interface. Device stability improves upon SAM modification, with efficiency decreasing only 20% after one month. Our work highlights a simple treatment route to achieve hysteresis-free, reproducible, stable, and highly efficient (16%) planar perovskite solar cells.

A Multifunctional Interlayer for Solution Processed High Performance Indium Oxide Transistors.

Multiple functionality of tungsten polyoxometalate (POM) has been achieved applying it as interfacial layer for solution processed high performance In2O3 thin film transistors, which results in overall improvement of device performance. This approach not only reduces off-current of the device by more than two orders of magnitude, but also leads to a threshold voltage reduction, as well as significantly enhances the mobility through facilitated charge injection from the electrode to the active layer. Such a mechanism has been elucidated through morphological and spectroscopic studies.

Effects of citric acid modified with fluoride, nano-hydroxyapatite and casein on eroded enamel.

OBJECTIVES: The aim of this in vitro study was to evaluate the effects of citric acid containing fluoride, nano-hydroxyapatite, and casein on eroded enamel. DESIGN: The crowns of 120 extracted bovine incisors were embedded in acrylic resin. An enamel window (2 × 3 mm) was created on the surface. Before in vitro pellicle formation samples were eroded in 1% citric acid (pH = 3.2) for 1 h at 36 °C and were randomly classified to eight groups (n = 15) as follows: Positive control: 1% citric acid, Negative control: Distilled water, F1: 0.047 mmol/L sodium fluoride, F2: 0.071 mmol/L sodium fluoride, NHA1: %0.05 Nano-Hydroxyapatite, NHA2: %0.1 Nano-Hydroxyapatite, C1: %0.02 Casein, C2: %0.2 Casein. Erosion cycling was performed three times daily for 3 days. In each cycle, the samples were immersed in 10 mL of control or modified solutions (10 min) and in 10 mL of artificial saliva (60 min). The surface roughness and enamel loss were analyzed by using profilometer, scanning electron microscopy (SEM) and atomic force microscopy techniques (AFM). RESULTS: Among the groups, the positive control group was found to be having the highest erosive wear. Erosive wear in the F2, NHA2, C1, and C2 groups was not significantly different from the negative control group (p > 0.05). The C1 and C2 groups showed that erosion terminated and minimal tissue recovery occurred on the enamel surface. CONCLUSION: Although all modifications reduced further demineralization, the citric acid modification with casein was found to be having a greater impact on dental erosion than the others.

Biofunctionalized conductive polymers enable efficient CO2 electroreduction.

Selective electrocatalysts are urgently needed for carbon dioxide (CO2) reduction to replace fossil fuels with renewable fuels, thereby closing the carbon cycle. To date, noble metals have achieved the best performance in energy yield and faradaic efficiency and have recently reached impressive electrical-to-chemical power conversion efficiencies. However, the scarcity of precious metals makes the search for scalable, metal-free, CO2 reduction reaction (CO2RR) catalysts all the more important. We report an all-organic, that is, metal-free, electrocatalyst that achieves impressive performance comparable to that of best-in-class Ag electrocatalysts. We hypothesized that polydopamine-a conjugated polymer whose structure incorporates hydrogen-bonded motifs found in enzymes-could offer the combination of efficient electrical conduction, together with rendered active catalytic sites, and potentially thereby enable CO2RR. Only by developing a vapor-phase polymerization of polydopamine were we able to combine the needed excellent conductivity with thin film-based processing. We achieve catalytic performance with geometric current densities of 18 mA cm-2 at 0.21 V overpotential (-0.86 V versus normal hydrogen electrode) for the electrosynthesis of C1 species (carbon monoxide and formate) with continuous 16-hour operation at >80% faradaic efficiency. Our catalyst exhibits lower overpotentials than state-of-the-art formate-selective metal electrocatalysts (for example, 0.5 V for Ag at 18 mA cm-1). The results confirm the value of exploiting hydrogen-bonded sequences as effective catalytic centers for renewable and cost-efficient industrial CO2RR applications.

Low Work Function Lacunary Polyoxometalates as Electron Transport Interlayers for Inverted Polymer Solar Cells of Improved Efficiency and Stability.

Effective interface engineering has been shown to play a vital role in facilitating efficient charge-carrier transport, thus boosting the performance of organic photovoltaic devices. Herein, we employ water-soluble lacunary polyoxometalates (POMs) as multifunctional interlayers between the titanium dioxide (TiO2) electron extraction/transport layer and the organic photoactive film to simultaneously enhance the efficiency, lifetime, and photostability of polymer solar cells (PSCs). A significant reduction in the work function (WF) of TiO2 upon POM utilization was observed, with the magnitude being controlled by the negative charge of the anion and the selection of the addenda atom (W or Mo). By inserting a POM interlayer with ∼10 nm thickness into the device structure, a significant improvement in the power conversion efficiency was obtained; the optimized POM-modified poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2- 33 ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]]:[6,6]-phenyl-C70 butyric acid methyl ester (PTB7:PC70BM)-based PSCs exhibited an efficiency of 8.07%, which represents a 21% efficiency enhancement compared to the reference TiO2 cell. Similar results were obtained in POM-modified devices based on poly(3-hexylthiophene) (P3HT) with electron acceptors of different energy levels, such as PC70BM or indene-C60 bisadduct (IC60BA), which enhanced their efficiency up to 4.34 and 6.21%, respectively, when using POM interlayers; this represents a 25-33% improvement as compared to the reference cells. Moreover, increased lifetime under ambient air and improved photostability under constant illumination were observed in POM-modified devices. Detailed analysis shows that the improvements in efficiency and stability synergistically stem from the reduced work function of TiO2 upon POM coverage, the improved nanomorphology of the photoactive blend, the reduced interfacial recombination losses, the superior electron transfer, and the more effective exciton dissociation at the photoactive layer/POM/TiO2 interfaces.

Improvement of Catalytic Activity by Nanofibrous CuInS2 for Electrochemical CO2 Reduction.

The current study reports the application of chalcopyrite semiconductor CuInS2 (CIS) nanofibers for the reduction of CO2 to CO with a remarkable Faradaic efficiency of 77 ± 4%. Initially the synthesis of CuInS2 nanofibers was carried out by adaptable electrospinning technique. To reduce the imperfection in the crystalline fiber, polyacrylonitrile (PAN) was selected as template polymer. Afterward, the desired chemical structure of nanofibers was achieved through sulfurization process. Making continuous CuInS2 nanofibers on the cathode surface by the electrospinning method brings the advantages of being economical, environmentally safe, and versatile. The obtained nanofibers of well investigated size and diameter according to the SEM (scanning electron microscope) were used in electrochemical studies. An improvement of Faradaic efficiency was achieved with the catalytic active CuInS2 in nanofibrous structure as compared to the solution processed CuInS2. This underlines the important effect of the electrode fabrication on the catalytic performance. Being less contaminated as compared to solution processing, and having a well-defined composition and increased catalytically active area, the CuInS2 nanofiber electrodes prepared by the electrospinning technique show a 4 times higher Faradaic efficiency. Furthermore, in this study, attention was paid to the stability of the CuInS2 nanofiber electrodes. The electrochemical reduction of CO2 to CO by using CIS nanofibers coated onto FTO electrodes was carried out for 10 h in total. The observed current density of 0.22 mA cm-2 and the stability of CIS nanofiber electrodes are found to be competitive with other heterogeneous electrocatalysts. Hence, we believe that the fabrication and application of nanofibrous materials through the electrospinning technique might be of interest for electrocatalytic studies in CO2 reduction.

Penternary chalcogenides nanocrystals as catalytic materials for efficient counter electrodes in dye-synthesized solar cells.

The penternary chalcogenides Cu2CoSn(SeS)4 and Cu2ZnSn(SeS)4 were successfully synthesized by hot-injection method, and employed as a catalytic materials for efficient counter electrodes in dye-synthesized solar cells (DSSCs). The structural, compositional, morphological and optical properties of these pentenary semiconductors were characterized by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), energy-dispersive spectrometer (EDS) and ultraviolet-visible (UV-Vis) spectroscopy. The Cu2CoSn(SeS)4 and Cu2ZnSn(SeS)4 nanocrystals had a single crystalline, kesterite phase, adequate stoichiometric ratio, 18-25 nm particle sizes which are forming nanospheres, and band gap energy of 1.18 and 1.45 eV, respectively. Furthermore, the electrochemical impedance spectroscopy and cyclic voltammograms indicated that Cu2CoSn(SeS)4 nanocrystals as counter electrodes exhibited better electrocatalytic activity for the reduction of iodine/iodide electrolyte than that of Cu2ZnSn(SeS)4 nanocrystals and conventional platinum (Pt). The photovoltaic results demonstrated that DSSC with a Cu2CoSn(SeS)4 nanocrystals-based counter electrode achieved the best efficiency of 6.47%, which is higher than the same photoanode employing a Cu2ZnSn(SeS)4 nanocrystals (3.18%) and Pt (5.41%) counter electrodes. These promising results highlight the potential application of penternary chalcogen Cu2CoSn(SeS)4 nanocrystals in low-cost, high-efficiency, Pt-free DSSCs.

Photocatalytic hydrogen evolution by oleic acid-capped CdS, CdSe, and CdS0.75Se0.25 alloy nanocrystals.

Photocatalytic generation of hydrogen by using oleic acid-capped CdS, CdSe, and CdS(0.75)Se(0.25) alloy nanocrystals (quantum dots) has been investigated under visible-light irradiation by employing Na(2)S and Na(2)SO(3) as hole scavengers. Highly photostable CdS(0.75)Se(0.25) alloy nanocrystals gave the highest hydrogen evolution rate (1466 µmol h(-1) g(-1)), which was about three times higher than that of CdS and seven times higher than that of CdSe.

Preparation of MIP-based QCM nanosensor for detection of caffeic acid.

In the present work, a new caffeic acid imprinted quartz crystal microbalance (QCM) nanosensor has been designed for selective assignation of caffeic acid in plant materials. Methacrylamidoantipyrine-iron(III) [MAAP-Fe(III)] as metal-chelating monomer has been used to prepare selective molecular imprinted polymer (MIP). MIP film for detection of caffeic acid has been developed on QCM electrode and selectivity experiments and analytical performance of caffeic acid imprinted QCM nanosensor has been studied. The caffeic acid imprinted QCM nanosensor has been characterized by AFM. After the characterization studies, imprinted and non-imprinted nanosensors was connected to QCM system for studies of connection of the target molecule, selectivity and the detection of amount of target molecule in real samples. The detection limit was found to be 7.8 nM. The value of Langmuir constant (b) (4.06 × 10(6)) that was acquired using Langmuir graph demonstrated that the affinity of binding sites was strong. Also, selectivity of prepared caffeic acid imprinted nanosensor was found as being high compared to chlorogenic acid. Finally, the caffeic acid levels in plant materials was determined by the prepared QCM nanosensor.

Attachment, proliferation and collagen type I mRNA expression of human gingival fibroblasts on different biodegradable membranes.

The purpose of this study was to investigate adhesion, proliferation and type I collagen (COL I) mRNA expression of gingival fibroblasts on different membranes used in periodontal applications. Collagen (C), acellular dermal matrix (ADM) and polylactic acid; polyglycolic acid; lactide/glycolide copolymer (PLGA) biodegradable membranes were combined with gingival fibroblasts in culture and incubated for 48 h. Cell adhesion was examined with scanning electron and confocal microscopy. MTT assay was used to measure proliferation. COL I mRNA expression was assessed using quantitative-polymerase chain reaction (QPCR). The PLGA group exhibited the lowest cell survival on day 5 and 10, and lowest cell proliferation on days 5, 10 and 14. While cell proliferation was similar in C and ADM groups, the C membrane showed a slightly greater increase in viable cells to day 10. Confocal and scanning electron microscopy confirmed the results of proliferation and MTT assays. The highest COL I mRNA expression was noted in the PLGA membrane group when compared to the C (p < 0.01) and ADM (p < 0.05) membrane groups. These data revealed that adherence and proliferation of primary gingival fibroblasts on collagen-based C and ADM membranes is better than that seen with PLGA membranes, and thus may be preferable in the treatment of gingival recession defects.

Humidity adsorption kinetics of calix[4]arene derivatives measured using QCM technique.

This study focuses on the characterization of sulphonated calix[4]arene derivative films coated on a quartz substrate with a thickness of 40 nm by spin coating method for humidity detection. The humidity adsorption kinetics of the sulphonated calix[4]arene films was investigated by quartz crystal microbalance (QCM) technique. The Langmuir model was used to determine the adsorption rates and Gibbs free energy for various relative humidities between 11% and 97%. Our reproducible experimental results show that suphonated calix[4]arene films have a great potential for humidity sensing applications at room temperature operations.

Adsorption of dyes on Sahara desert sand.

Sahara desert sand (SaDeS) was employed as a mineral sorbent for retaining organic dyes from aqueous solutions. Natural sand has demonstrated a strong affinity for organic dyes but significantly lost its adsorption capacity when it was washed with water. Therefore, characterization of both natural and water washed sand was performed by XRD, BET, SEM and FTIR techniques. It was found that water-soluble kyanite, which is detected in natural sand, is the dominant factor affecting adsorbance of cationic dyes. The sand adsorbs over 75% of cationic dyes but less than 21% for anionic ones. Among the dyes studied, Methylene Blue (MB) demonstrated the strongest affinity for Sahara desert sand (Q(e)=11.98 mg/g, for initial dye solution concentration 3.5 x 10(-5)mol/L). The effects of initial dye concentration, the amount of the adsorbent, the temperature and the pH of the solution on adsorption capacity were tested by using Methylene Blue as model dye. Pseudo-first-order, pseudo-second-order and intraparticle diffusion models were applied. It was concluded that adsorption of Methylene Blue on Sahara desert sand followed pseudo-second order kinetics. Gibbs free energy, enthalpy change and entropy change were calculated and found -6411 J/mol, -30360 J/mol and -76.58 J/mol K, respectively. These values indicate that the adsorption is an exothermic process and has a spontaneous nature at low temperatures.