Sensing Of Aqueous Phosphates By Polymers With Dual Modes Of Signal Transduction

A new approach to sensing of aqueous phosphate-related anions based on chromogenic conductive polymers is demonstrated. This method utilizes synergy between low-level p-doping in a polythiophene polymer and hydrogen bonding to increase anion-sensor affinity. These chromogenic conductive polymers show anion-specific changes both in color and in conductivity upon increasing concentration of anions, thus providing two independent modes of signal transduction

Benzothiadiazoles And Dipyrrolyl Quinoxalines With Extended Conjugated Chromophores-fluorophores And Anion Sensors

Stable fluorescent chromophores find use in a growing number of practical applications, including their utility as laser dyes,1 emitters in light-emitting diodes,2 photoconductors,3 optical data storage,4 and optical switches.5 Stable fluorophores with high quantum yields are widely used in fluorescent sensors6 and labels.7 These became very popular lately, owing to their potential for high sensitivity at low concentration coupled with decreased cost of the required equipment.8 Recently, we have described a new class of fluorescent anion sensors bearing extended conjugated chromophores9 with incorporated 2,3-di(1H-2-pyrrolyl)quinoxaline, (DPQ), as the anion recognition element.10 Literature shows that DPQ binds anions via hydrogen bonding between pyrrole NH and anions, the hydrogen bonding nature of the DPQ−anion complex was demonstrated by 1H NMR.10a In this paper, we provide a full account of our efforts including synthesis and photophysical properties of DPQ-based fluorescent anion sensors with extended conjugated chromophores S1−S6 (Figure 1), including their benzothiadiazole precursors F1−F6, which appears to be an interesting set of highly stable fluorescent chromophores

CuSCN Nanowires as Electrodes for p-Type Quantum Dot Sensitized Solar Cells: Charge Transfer Dynamics and Alumina Passivation

Quantum dot sensitized solar cells (QDSSCs) are a promising photovoltaic technology due to their low cost and simplicity of fabrication. Most QDSSCs have an n-type configuration with electron injection from QDs into TiO2, which generally leads to unbalanced charge transport (slower hole transfer rate) limiting their efficiency and stability. We have previously demonstrated that p-type (inverted) QD sensitized cells have the potential to solve this problem. Here we show for the first time that electrodeposited CuSCN nanowires can be used as a p-type nanostructured electrode for p-QDSSCs. We demonstrate their efficient sensitization by heavy metal free CuInSxSe2-x quantum dots. Photophysical studies show efficient and fast hole injection from the excited QDs into the CuSCN nanowires. The transfer rate is strongly time dependent but the average rate of 2.5 × 109 s–1 is much faster than in previously studied sensitized systems based on NiO. Moreover, we have developed an original experiment allowing us to calculate independently the rates of charge injection and QD regeneration by the electrolyte and thus to determine which of these processes occurs first. The average QD regeneration rate (1.3 × 109 s–1) is in the same range as the hole injection rate, resulting in an overall balanced charge separation process. To reduce recombination in the sensitized systems and improve their stability, the CuSCN nanowires were coated with thin conformal layers of Al2O3 using atomic layer deposition (ALD) and fully characterized by XPS and EDX. We demonstrate that the alumina layer protects the surface of CuSCN nanowires, reduces charge recombination, and increases the overall charge transfer rate up to 1.5 times depending on the thickness of the deposited Al2O3 layer

CuSCN nanowires as electrodes for p-type quantum dot sensitized solar cells : charge transfer dynamics and alumina passivation

Funding: European Research Council (grant number 321305) and the EPSRC (grant numbers EP/L017008/1 and EP/M506631/1). IDWS is a Royal Society Wolfson Research Merit award holder.Quantum dot sensitized solar cells (QDSSCs) are a promising photovoltaic technology due to their low cost and simplicity of fabrication. Most QDSSCs have an n-type configuration with electron injection from QDs into TiO2, which generally leads to unbalanced charge transport (slower hole transfer rate) limiting their efficiency and stability. We have previously demonstrated that p-type (inverted) QD sensitized cells have the potential to solve this problem. Here we show for the first time that electrodeposited CuSCN nanowires can be used as a p-type nanostructured electrode for p-QDSSCs. We demonstrate their efficient sensitization by heavy metal free CuInSxSe2-x quantum dots. Photophysical studies show efficient and fast hole injection from the excited QDs into the CuSCN nanowires. The transfer rate is strongly time dependent but the average rate of 2.5 x 109 s-1 is much faster than in previously studied sensitized systems based on NiO. Moreover, we have developed an original experiment allowing us to calculate independently the rates of charge injection and QD regeneration by the electrolyte and thus to determine which of these processes occurs first. The average QD regeneration rate (1.33 x 109 s-1 ) is in the same range as the hole injection rate, resulting in an overall balanced charge separation process. To reduce recombination in the sensitized systems and improve their stability, the CuSCN nanowires were coated with thin conformal layers of Al2O3 using atomic layer deposition (ALD) and fully characterized by XPS and EDX. We demonstrate that the alumina layer protects the surface of CuSCN nanowires, reduces charge recombination and increases the overall charge transfer rate up to 1.5 times depending on the thickness of the deposited Al2O3 layer.PostprintPeer reviewe

Properties of Electrodeposited CuSCN 2D Layers and Nanowires Influenced by Their Mixed Domain Structure

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Efficient eco-friendly inverted quantum dot sensitized solar cells

This work was supported by the Agence Nationale de la Recherche, project QuePhélec (ANR-13-BS10-0011-01). MTS and IDWS are thankful to ERC for financial support for exciton diffusion project, grant number 321305. AR and IDWS also acknowledge EPSRC for financial support (grant number EP/J009016). We also acknowledge funding from the Labex LANEF in Grenoble (ANR-10-LABX-51-01).Recent progress in quantum dot (QD) sensitized solar cells has demonstrated the possibility of low-cost and efficient photovoltaics. However, the standard device structure based on n-type materials often suffers from slow hole injection rate, which may lead to unbalanced charge transport. We have fabricated efficient p-type (inverted) QD sensitized cells, which combine the advantages of conventional QD cells with p-type dye sensitized configurations. Moreover, p-type QD sensitized cells can be used in highly promising tandem configurations with n-type ones. QDs without toxic Cd and Pb elements and with improved absorption and stability were successfully deposited onto mesoporous NiO electrode showing good coverage and penetration according to morphological analysis. Detailed photophysical charge transfer studies showed that high hole injection rates (108 s-1) observed in such systems are comparable with electron injection in conventional n-type QD assemblies. Inverted solar cells fabricated with various QDs demonstrate excellent power conversion efficiencies of up to 1.25%, which is 4 times higher than the best values for previous inverted QD sensitized cells. Attempts to passivate the surface of the QDs show that traditional methods of reduction of recombination in the QD sensitized cells are not applicable to the inverted architectures.Publisher PDFPeer reviewe

Safer-by-Design Fluorescent Nanocrystals: Metal Halide Perovskites vs Semiconductor Quantum Dots

International audienceDespite the young age of the research field, substantial progress has been made in the study of metal halide perovskite nanocrystals (HPNCs). Just as their thin-film counterparts are used for light absorption in solar cells, they are on the way to revolutionizing research on novel chromophores for light emission applications. Exciting physics arising from their peculiar structural, electronic, and excitonic properties are being discovered with breathtaking speed. Many things we have learned from the study of conventional semiconductor quantum dots (CSQDs) of II−VI (e.g., CdSe), IV−VI (e.g., PbS), and III−V (e.g., InP) compounds have to be thought over, as HPNCs behave differently. This Feature Article compares both families of nanocrystals and then focuses on approaches for substituting toxic heavy metals without sacrificing the unique optical properties as well as on surface coating strategies for enhancing the long-term stability

Organic/inorganic hybrid materials for optoelectronics

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Sensing of Aqueous Phosphates by Polymers with Dual Modes of Signal Transduction

A new approach to sensing of aqueous phosphate-related anions based on chromogenic conductive polymers is demonstrated. This method utilizes synergy between low-level p-doping in a polythiophene polymer and hydrogen bonding to increase anion-sensor affinity. These chromogenic conductive polymers show anion-specific changes both in color and in conductivity upon increasing concentration of anions, thus providing two independent modes of signal transduction

Ternary and quaternary metal chalcogenide nanocrystals: synthesis, properties and applications

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