High Electronic Coupling between Cu Complexes and Oxidized Dyes Confirmed by Measurements of Driving Force Dependent Regeneration Kinetics in Minimal Electrolyte System.

We confirm fast regeneration kinetics between copper complexes and oxidized organic dyes and the major contribution of electronic coupling (). The highest efficiency of dye-sensitized TiO solar cells has been shown by employing Cu complex redox couples. Various groups have reported a fast regeneration rate of oxidized dyes by Cu complexes giving a low driving force attributed to low reorganization energy (λ), but the effect of has not been evaluated.

Catalytic Decomposition of an Organic Electrolyte to Methane by a Cu Complex-Derived In Situ CO Reduction Catalyst.

Metal complexes are often transformed to metal complex-derived catalysts during electrochemical CO reduction, enhancing the catalytic performance of CO reduction or changing product selectivity. To date, it has not been investigated whether metal-complex derived catalysts also enhance the decomposition of the solvent/electrolyte components as compared to an uncoated electrode. Here, we tested the electrochemical stability of five organic solvent-based electrolytes with and without a Cu complex-derived catalyst on carbon paper in an inert atmosphere.

Effect of the Cu Redox Potential of Non-Macrocyclic Cu Complexes on Electrochemical CO Reduction.

Cu complexes facilitate the reduction of CO to valuable chemicals. The catalytic conversion likely involves the binding of CO and/or reduction intermediates to Cu, which in turn could be influenced by the electron density on the Cu ion. Herein we investigated whether modulating the redox potential of Cu complexes by changing their ligand structures influenced their CO reduction performance significantly.

Solvent-Dependent Functional Aggregates of Unsymmetrical Squaraine Dyes on TiO Surface for Dye-Sensitized Solar Cells.

Alkyl group wrapped donor-acceptor-donor (D-A-D) based unsymmetrical squaraine dyes , , and were used to evaluate the effect of sensitizing solvents on dye-sensitized solar cell (DSSC) efficiency. A drastic change in DSSC efficiency was observed when the photo-anodes were sensitized in acetonitrile (bad solvent when considering dye solubility) and chloroform (good solvent) with an Iodolyte (I/I) electrolyte. The DSSC device sensitized with squaraine dyes in acetonitrile showed better photovoltaic performance with enhanced photocurrent generation and photovoltage compared to the device sensitized in chloroform.

Insight into the Origin of Trapping in Polymer/Fullerene Blends with a Systematic Alteration of the Fullerene to Higher Adducts.

The bimolecular recombination characteristics of conjugated polymer poly[(4,4'-bis(2-ethylhexyl)dithieno[3,2-:2',3'-]silole)-2,6-diyl-alt-(2,5-bis 3-tetradecylthiophen-2-yl thiazolo 5,4- thiazole)-2,5diyl] (PDTSiTTz) blended with the fullerene series PC60BM, ICMA, ICBA, and ICTA have been investigated using microsecond and femtosecond transient absorption spectroscopy, in conjunction with electroluminescence measurements and ambient photoemission spectroscopy. The non-Langevin polymer PDTSiTTz allows an inspection of intrinsic bimolecular recombination rates uninhibited by diffusion, while the low oscillator strengths of fullerenes allow polymer features to dominate, and we compare our results to those of the well-known polymer Si-PCPDTBT. Using μs-TAS, we have shown that the trap-limited decay dynamics of the PDTSiTTz polaron becomes progressively slower across the fullerene series, while those of Si-PCPDTBT are invariant.

Enhanced interfacial electron transfer kinetics between Co complexes and organic dyes with free space near their backbone.

Fast electron transfer (ET) between surface-bound dye molecules and electron donor molecules dissolved in electrolytes with simultaneous reduction in recombination rates are crucial to improve the photon-to-electron conversion efficiency of photo-electrochemical technologies. Here, the electron transfer characteristics of a new dye molecule PX47 with only two alkyl chains placed in the anti configuration of the π-conjugated quarterthiophene backbone is studied. It is anticipated that the appropriate free space between the alkyl chains allowed the approach of the Co(c1-bpy) redox mediator to near the backbone of the dye anchored to a TiO electrode even at complete coverage of the TiO surface, thereby enhancing electronic coupling.

Flexible Polymer X-ray Detectors with Non-fullerene Acceptors for Enhanced Stability: Toward Printable Tissue Equivalent Devices for Medical Applications.

There is growing interest in the development of novel materials and devices capable of ionizing radiation detection for medical applications. Organic semiconductors are promising candidates to meet the demands of modern detectors, such as low manufacturing costs, mechanical flexibility, and a response to radiation equivalent to human tissue. However, organic semiconductors have typically been employed in applications that convert low energy photons into high current densities, for example, solar cells and LEDs, and thus existing design rules must be re-explored for ionizing radiation detection where high energy photons are converted into typically much lower current densities.

Multisample Correlation Reveals the Origin of the Photocurrent of an Unstable CuO Photocathode during CO Reduction.

The reliable characterization of the photoelectrochemical (PEC) performance of unstable photoelectrodes, often the simplest devices used as a baseline, is a huge challenge. By performing a correlation analysis of more than 100 parameters of CuO photocathodes electrodeposited under the same conditions, we discovered a strong positive correlation ( = 0.866) between the photocurrent in argon and the deposition current peak magnitude during electrodeposition, while a strong negative correlation ( = -0.

The impact of insufficient time resolution on dye regeneration lifetime determined using transient absorption spectroscopy.

Dye regeneration lifetimes of a combination of dyes and redox mediators were determined by two transient absorption (TA) spectrometers with 0.5 ns (sub-ns) and 6 ns (ns) time resolutions to elucidate the impact of insufficient time resolution on the measurements of dye regeneration kinetics in dye-sensitised semiconductor electrodes. Due to the disordered nature of the dye-sensitised electrodes, the dye regeneration lifetime is often characterised by half-decay time (τ1/2) of the initial signal magnitude.

Substrate-Dependent Electron-Transfer Rate of Mixed-Ligand Electrolytes: Tuning Electron-Transfer Rate without Changing Driving Force.

To meet various requirements for electron transfer (ET) at the substrate/electrolyte interface, mixed redox couples assigned to different functions have been applied. While in all studies the mixed redox species had different redox potentials, such redox systems inherently lose energy by ET between the species. We report interfacial ET kinetics employing mixed-ligand electrolytes based on Co complexes with mixtures of dimethyl- and dinonyl-substituted bipyridyl (bpy) ligands with the same redox potential.

Effects of Interfacial Layers on the Open Circuit Voltage of Polymer/Fullerene Bulk Heterojunction Devices Studied by Charge Extraction Techniques.

Interfacial layers are frequently used in organic solar cells performing various functions, including blocking surface recombination, improving selectivity of charge carrier extraction, modification of the work function of the contact materials, and enhancing light absorption within the photoactive layer through an optical cavity effect. The aim of this work is to investigate the origin of performance enhancement of bulk heterojunction solar cells using various electron and hole interfacial layers, with a particular focus on separating the contributions of work function modification and reduced recombination to the improvement of the open circuit voltage ( V). Solar cells using poly[ N-9'-hepta-decanyl-2,7-carbazole- alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)]:[6,6]-phenyl C-butyric acid methyl ester (1:4) active layers were prepared with a combination of polymeric, metal oxide, and polyelectrolyte electron and/or hole interfacial layers.

Exploiting Intermolecular Interactions between Alkyl-Functionalized Redox-Active Molecule Pairs to Enhance Interfacial Electron Transfer.

The strategies to enhance electron transfer rates between redox-active, light-harvesting molecules attached to semiconductor surfaces and redox mediators in solution by modifying molecular structure are not fully investigated yet. Therefore, the design of molecules with controlled electron transfer rates remains a challenge. The aims of this work are to quantify the effect of long alkyl chain substitution on the electron transfer from cobalt(II/III) tris(2,2'-bipyridine) to organic molecules containing carbazole and thiophene and to demonstrate that alkyl chains can be used to enhance electron transfer between donor-acceptor pairs.

Quantitative characterisation of conductive fibers by capacitive coupling.

This work presents a study on a capacitively coupled contactless conductivity detector (C4D) for micron-sized fibers. Following a previous report on the qualitative application of C4D for fibers, the present study provides a thorough analysis of the signal response to fiber conductivity. Using reduced graphene oxide (RGO) fibers, the detector response as a function of fiber length, cross-sectional area and resistance has been investigated.

Enhancement of dye regeneration kinetics in dichromophoric porphyrin-carbazole triphenylamine dyes influenced by more exposed radical cation orbitals.

Reduction kinetics of oxidized dyes absorbed on semiconductor surfaces and immersed in redox active electrolytes has been mainly modeled based on the free energy difference between the oxidation potential of the dye and the redox potential of the electrolyte. Only a few mechanisms have been demonstrated to enhance the kinetics by other means. In this work, the rate constant of the reduction of oxidized porphyrin dye is enhanced by attaching non-conjugated carbazole triphenylamine moiety using iodine/triiodide and tris(2,2'-bispyridinium)cobalt II/III electrolytes.

Characterisation of graphene fibres and graphene coated fibres using capacitively coupled contactless conductivity detector.

The use of capacitively coupled contactless conductivity detection (C(4)D) for the characterisation of thin conductive graphene fibres, graphene composite fibres, and graphene coated fibrous materials is demonstrated for the first time. Within a few seconds, the non-destructive C(4)D detector provides a profile of the longetudinal physical homogeneity of the fibre, as well as extra information regarding fibre mophology and composition. In addition to the theoretical considerations related to the factors affect the output signal, this work evaluates the properties of graphene fibres using scanning C(4)D following the manufacturing process of wet-spinning.

Trap-Assisted Transport and Non-Uniform Charge Distribution in Sulfur-Rich PbS Colloidal Quantum Dot-based Solar Cells with Selective Contacts.

This study reports evidence of dispersive transport in planar PbS colloidal quantum dot heterojunction-based devices as well as the effect of incorporating a MoO3 hole selective layer on the charge extraction behavior. Steady state and transient characterization techniques are employed to determine the complex recombination processes involved in such devices. The addition of a selective contact drastically improves the device efficiency up to 3.

Enhanced Electron Lifetimes in Dye-Sensitized Solar Cells Using a Dichromophoric Porphyrin: The Utility of Intermolecular Forces.

Electron lifetimes in dye-sensitized solar cells employing a porphyrin dye, an organic dye, a 1:1 mixture of the two dyes, and a dichromophoric dye design consisting of the two dyes using a nonconjugated linker were measured, suggesting that the dispersion force of the organic dyes has a significant detrimental effect on the electron lifetime and that the dichromophoric design can be utilized to control the effect of the dispersion force.

An intermediate band dye-sensitised solar cell using triplet-triplet annihilation.

A new mechanism of charge photogeneration is demonstrated for the first time, based on organic molecular structures. This intermediate band approach, integrated into a dye-sensitised solar cell configuration is shown to generate charges upon illumination with low energy photons. Specifically 610 nm photoexcitation of Pt porphyrins, through a series of energy transfer steps and triplet-triplet annihilation, excites a higher energy absorption onset molecule, which is then capable of charge injection into TiO2.

A nonconjugated bridge in dimer-sensitized solar cells retards charge recombination without decreasing charge injection efficiency.

Dye sensitized solar cells (DSSCs) employing a dimer porphyrin, which was synthesised with two porphyrin units connected without conjugation, have shown that both porphyrin components can contribute to photocurrent generation, that is, more than 50 % internal quantum efficiency. In addition, the open-circuit voltage (Voc) of the DSSCs was higher than that of DSSCs using monomer porphyrins. In this paper, we first optimized cell structure and fabrication conditions.

Dye-Sensitized Solar Cell with Integrated Triplet-Triplet Annihilation Upconversion System.

Photon upconversion (UC) by triplet-triplet annihilation (TTA-UC) is employed in order to enhance the response of solar cells to sub-bandgap light. Here, we present the first report of an integrated photovoltaic device, combining a dye-sensitized solar cell (DSC) and TTA-UC system. The integrated device displays enhanced current under sub-bandgap illumination, resulting in a figure of merit (FoM) under low concentration (3 suns), which is competitive with the best values recorded to date for nonintegrated systems.

Dye regeneration kinetics in dye-sensitized solar cells.

The ideal driving force for dye regeneration is an important parameter for the design of efficient dye-sensitized solar cells. Here, nanosecond laser transient absorption spectroscopy was used to measure the rates of regeneration of six organic carbazole-based dyes by nine ferrocene derivatives whose redox potentials vary by 0.85 V, resulting in 54 different driving-force conditions.

Porphyrins for dye-sensitised solar cells: new insights into efficiency-determining electron transfer steps.

Porphyrin molecules offer immense potential as the light harvesting component of dye-sensitised nanocrystalline TiO(2) solar cells. Synthetic porphyrin dyes were amongst the first dyes trialled for sensitisation of inorganic semiconducting oxides. Today, they exhibit the best performance reported for dye-sensitised solar cells.

Carbon nanotube/graphene nanocomposite as efficient counter electrodes in dye-sensitized solar cells.

We demonstrated the replacement of the Pt catalyst normally used in the counter electrode of a dye-sensitized solar cell (DSSC) by a nanocomposite of dry spun carbon multi-walled nanotube (MWNT) sheets with graphene flakes (Gr-F). The effectiveness of this counter electrode on the reduction of the triiodide in the iodide/triiodide redox (I(-)/I(3)(-)) redox reaction was studied in parallel with the use of the dry spun carbon MWNT sheets alone and graphene flakes used independent of each other. This nanocomposite deposited onto fluorinated tin-oxide-coated glass showed improved catalytic behavior and power conversion efficiency (7.

Aqueous dye-sensitized solar cell electrolytes based on the ferricyanide-ferrocyanide redox couple.

Solar energy conversion efficiencies of over 4% have been achieved in DSCs constructed with aqueous electrolytes based on the ferricyanide-ferrocyanide redox couple, thereby avoiding the use of expensive, flammable and toxic solvents. This paradigm shift was made possible by the use of a hydrophobic organic carbazole dye.

Sodium fluoride-assisted modulation of anodized TiO₂ nanotube for dye-sensitized solar cells application.

This work reports the use of sodium fluoride (in ethylene glycol electrolyte) as the replacement of hydrofluoric acid and ammonium fluoride to fabricate long and perpendicularly well-aligned TiO₂ nanotube (TNT) (up to 21 μm) using anodization. Anodizing duration, applied voltage and electrolyte composition influenced the geometry and surface morphologies of TNT. The growth mechanism of TNT is interpreted by analyzing the current transient profile and the total charge density generated during anodization.