White Light to Near-IR Chargeable Single Component Photocapacitor Based on Donor-chromophore-Acceptor Dyes.

Power sources that can be charged anytime and anywhere are highly desirable for mobile devices. The most suitable device for achieving such wireless charging is a photocapacitor, which utilizes light as a renewable energy source instead of electricity from the grid. Sunlight on Earth is intermittent and unstable, so photocapacitors that can be charged by the day or room light and near-infrared (near-IR) radiation are needed to ensure the uninterrupted operation of the equipment. We employ a single dye-sensitized solar cell as a photocapacitor without adding any additional charge storage components to reduce the cost and complexity of device manufacturing. To realize such photocapacitors, this work presents a family of new isoindigo-based D-π-A photoactive dyes with good visible and near-IR absorption. Notably, LF15 has a higher molar absorbance coefficient and enhanced dye-loading than LF23, which is consistent with the higher photocurrent of photocapacitors based on the former. Photocapacitors based on these three dyes achieve photovoltages up to 0.74 V, area-specific capacitances of 2.87 mF cm-2 , and excellent charge-discharge stability. The devices can be charged in both visible and near-IR conditions, exhibiting typical capacitor behavior.

Illumination Time Dependent Learning in Dye Sensitized Solar Cells.

Learning through vision is an essential skill for intelligent machines. In an attempt to implement this highly complex feature at low energy cost, a dye-sensitized solar cell is proposed that learns using illumination time as a cue. Particularly, the device alters its photocurrent and memorizes this change in dependence of light exposure duration. This behavior parallels synaptic learning that also requires continuous or repeated electrical stimuli as triggers. Therefore, such optically learning solar cells may serve as promising building blocks in optoelectronic neural networks, potentially enabling visually learning electronics operating at negligible energy consumption and minimal hardware complexity.

A Stable Blue Photosensitizer for Color Palette of Dye-Sensitized Solar Cells Reaching 12.6% Efficiency.

We report a blue dye, coded as R6, which features a polycyclic aromatic hydrocarbon, 9,19-dihydrobenzo[1',10']phenanthro[3',4':4,5]thieno[3,2-b]benzo[1,10]phenanthro[3,4-d]thiophene, coupled with a diarylamine electron donor and 4-(7-ethynylbenzo[c][1,2,5]thiadiazol-4-yl)benzoic acid acceptor. Dye R6 displays a brilliant sapphire color in a sensitized TiO2 mesoporous film with a Co(II/III) tris(bipyridyl)-based redox electrolyte. The R6 based dye-sensitized solar cell achieves an impressive power conversion efficiency of 12.6% under standard air mass 1.5 global, 100 mW cm-2, and shows a remarkable photostability.

Enhancing the stability of porphyrin dye-sensitized solar cells by manipulation of electrolyte additives.

The use of porphyrin-based photosensitizers with superior light-harvesting properties has enabled the power conversion efficiency of dye-sensitized solar cells (DSCs) to reach 13 % under full sun illumination. However, a major limitation of such devices corresponds to the volatility of the solvent used so far for the electrolyte, which prevents practical applications. In this work, we describe a porphyrin-ionic liquid DSC, which not only affords the highest efficiency reported to date, but is also stable for more than 300 h under continuous full sun illumination at 60 °C. Furthermore, we identify a previously unreported pathway for device degradation, and show that the addition of N-methylbenzimidazole and a thiocyanate salt to the electrolyte is critical to obtaining long-lived devices.

Highly stable dye-sensitized solar cells based on novel 1,2,3-triazolium ionic liquids.

We describe the design and synthesis of novel low viscosity bicyclic 1,2,3-triazolium ionic liquids. These new salts are applied as nonvolatile electrolytes in dye-sensitized solar cells, affording efficiencies up to 7.07% at low light intensities, and 6.00% when illuminated at 100 mW cm(-2). The devices are highly stable, retaining ca. 90% of their initial performance even after 1000 h of sun testing at 60 °C. The results obtained with these new ionic liquids compare very favorably to benchmark ionic liquid-based devices and illustrate the potential of the triazolium family of salts to compete with their imidazolium counterparts.

Influence of structural variations in push-pull zinc porphyrins on photovoltaic performance of dye-sensitized solar cells.

We designed and synthesized two new zinc porphyrin dyes for dye-sensitized solar cells (DSCs). Subtle molecular structural variation in the dyes significantly influenced the performance of the DSC devices. By utilizing these dyes in combination with a cobalt-based redox electrolyte using a photoanode made of mesoporous TiO2 , we achieved a power conversion efficiency (PCE) of up to 12.0 % under AM 1.5 G (100 mW cm(-2)) simulated solar light. Moreover, we obtained a high PCE of 6.4 % for solid-state dye-sensitized solar cells by using 2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene as a hole-transporting material.

Solid-State Organization and Ambipolar Field-Effect Transistors of Benzothiadiazole-Cyclopentadithiophene Copolymer with Long Branched Alkyl Side Chains.

The solid-state organization of a benzothiadiazole-cyclopentadithiophene copolymer with long, branched decyl-tetradecyl side chains (CDT-BTZ-C14,10) is investigated. The C14,10 substituents are sterically demanding and increase the π-stacking distance to 0.40 nm from 0.37 nm for the same polymer with linear hexadecyls (C16). Despite the bulkiness, the C14,10 side chains tend to crystallize, leading to a small chain-to-chain distance between lamellae stacks and to a crystal-like microstructure in the thin film. Interestingly, field-effect transistors based on solution processed layers of CDT-BTZ-C14,10 show ambipolar behavior in contrast to CDT-BTZ-C16 with linear side chains, for which hole transport was previously observed. Due to the increased π-stacking distance, the mobilities are only 6 × 10-4 cm²/Vs for electrons and 6 × 10-5 cm²/Vs for holes, while CDT-BTZ-C16 leads to values up to 5.5 cm²/Vs. The ambipolarity is attributed to a lateral shift between stacked backbones provoked by the bulky C14,10 side chains. This reorganization is supposed to change the transfer integrals between the C16 and C14,10 substituted polymers. This work shows that the electronic behavior in devices of one single conjugated polymer (in this case CDT-BTZ) can be controlled by the right choice of the substituents to place the backbones in the desired packing.

Avoiding diffusion limitations in cobalt(III/II)-tris(2,2'-bipyridine)-based dye-sensitized solar cells by tuning the mesoporous TiO2 film properties.

Dye-sensitized solar cells based on electrolytes containing cobalt complexes as redox shuttles typically suffer a major limitation in terms of slow diffusion of those couples through the mesoporous TiO(2) film. This results in a drop of the photocurrent density, particularly at high incident light intensities, reducing the overall cell performance. This work illustrates how tuning the four characteristic parameters of the mesoporous TiO(2) layer, namely film thickness, particle size, pore size and porosity, by simply optimizing the TiCl(4) post-treatment, completely eliminates diffusion problems of cobalt(III/II) tris(2,2'-bipyridine) and at the same time maximizes the short-circuit photocurrent density. As a result, a power conversion efficiency of 10.0% at AM 1.5 G 100 mW cm(-2) was reached in conjunction with an organic sensitizer.

Fine-tuning the electronic structure of organic dyes for dye-sensitized solar cells.

A series of metal-free organic dyes exploiting different combinations of (hetero)cyclic linkers (benzene, thiophene, and thiazole) and bridges (4H-cyclopenta[2,1-b:3,4-b']dithiophene (CPDT) and benzodithiophene (BDT)) as the central π-spacers were synthesized and characterized. Among them, the sensitizer containing the thiophene and CPDT showed the most broad incident photon-to-current conversion efficiency spectra, resulting in a solar energy conversion efficiency (η) of 6.6%.

Synthetic principles directing charge transport in low-band-gap dithienosilole-benzothiadiazole copolymers.

Given the fundamental differences in carrier generation and device operation in organic thin-film transistors (OTFTs) and organic photovoltaic (OPV) devices, the material design principles to apply may be expected to differ. In this respect, designing organic semiconductors that perform effectively in multiple device configurations remains a challenge. Following "donor-acceptor" principles, we designed and synthesized an analogous series of solution-processable π-conjugated polymers that combine the electron-rich dithienosilole (DTS) moiety, unsubstituted thiophene spacers, and the electron-deficient core 2,1,3-benzothiadiazole (BTD). Insights into backbone geometry and wave function delocalization as a function of molecular structure are provided by density functional theory (DFT) calculations at the B3LYP/6-31G(d,p) level. Using a combination of X-ray techniques (2D-WAXS and XRD) supported by solid-state NMR (SS-NMR) and atomic force microscopy (AFM), we demonstrate fundamental correlations between the polymer repeat-unit structure, molecular weight distribution, nature of the solubilizing side-chains appended to the backbones, and extent of structural order attainable in p-channel OTFTs. In particular, it is shown that the degree of microstructural order achievable in the self-assembled organic semiconductors increases largely with (i) increasing molecular weight and (ii) appropriate solubilizing-group substitution. The corresponding field-effect hole mobilities are enhanced by several orders of magnitude, reaching up to 0.1 cm(2) V(-1) s(-1) with the highest molecular weight fraction of the branched alkyl-substituted polymer derivative in this series. This trend is reflected in conventional bulk-heterojunction OPV devices using PC(71)BM, whereby the active layers exhibit space-charge-limited (SCL) hole mobilities approaching 10(-3) cm(2) V(-1) s(-1), and yield improved power conversion efficiencies on the order of 4.6% under AM1.5G solar illumination. Beyond structure-performance correlations, we observe a large dependence of the ionization potentials of the polymers estimated by electrochemical methods on polymer packing, and expect that these empirical results may have important consequences on future material study and device applications.

Porphyrin-sensitized solar cells with cobalt (II/III)-based redox electrolyte exceed 12 percent efficiency.

The iodide/triiodide redox shuttle has limited the efficiencies accessible in dye-sensitized solar cells. Here, we report mesoscopic solar cells that incorporate a Co((II/III))tris(bipyridyl)-based redox electrolyte in conjunction with a custom synthesized donor-π-bridge-acceptor zinc porphyrin dye as sensitizer (designated YD2-o-C8). The specific molecular design of YD2-o-C8 greatly retards the rate of interfacial back electron transfer from the conduction band of the nanocrystalline titanium dioxide film to the oxidized cobalt mediator, which enables attainment of strikingly high photovoltages approaching 1 volt. Because the YD2-o-C8 porphyrin harvests sunlight across the visible spectrum, large photocurrents are generated. Cosensitization of YD2-o-C8 with another organic dye further enhances the performance of the device, leading to a measured power conversion efficiency of 12.3% under simulated air mass 1.5 global sunlight.

Ultrahigh mobility in polymer field-effect transistors by design.

In this article, the design paradigm involving molecular weight, alkyl substituents, and donor-acceptor interaction for the poly[2,6-(4,4-bis-alkyl-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (cyclopentadithiophene-benzothiadiazole) donor-acceptor copolymer (CDT-BTZ) toward field-effect transistors (FETs) with ultrahigh mobilities is presented and discussed. It is shown that the molecular weight plays a key role in improving hole mobilities, reaching an exceptionally high value of up to 3.3 cm(2) V(-1) s(-1). Possible explanations for this observation is highlighted in conjunction with thin film morphology and crystallinity. Hereby, it is found that the former does not change, whereas, at the same time, crystallinity improved with ever growing molecular weight. Furthermore, other important structural design factors such as alkyl chain substituents and donor-acceptor interaction between the polymer backbones potentially govern intermolecular stacking distances crucial for charge transport and hence for device performance. In this aspect, for the first time we attempt to shed light onto donor-acceptor interactions between neighboring polymer chains with the help of solid state nuclear magnetic resonance (NMR). On the basis of our results, polymer design principles are inferred that might be of relevance for prospective semiconductors exhibiting hole mobilities even exceeding 3 cm(2) V(-1) s(-1).

Improving polymer transistor performance via morphology control.

In this tutorial review, different film microstructures, commonly termed morphologies, into which the organic semiconductor polymers self-assemble macroscopically are presented, together with their corresponding influence on charge carrier mobility and hence transistor behaviour. It will be clarified how various chemical design approaches and solution processing methods enable the manipulation of polymer morphology, leading to improvements in transistor performance. Ultimately, it is illustrated that the directional alignment of polymers form oriented fiber-like films, yielding one of the highest mobilities reported so far for polymer transistors. Based on these observations, a prediction is made concerning which kind of morphology is expected to reach the best charge carrier mobility.

Tailoring structure-property relationships in dithienosilole-benzothiadiazole donor-acceptor copolymers.

Four new DTS-BTD copolymers (P1-P4) differing by the concentration of electron-donating and -withdrawing substituents along the backbone have been synthesized and characterized by 2D-WAXS and in bottom-contact FETs. While all copolymers can self-assemble into lamellar superstructures, only P2 and P4 show a propensity to pi-stack. P4 exhibits a hole mobility as high as 0.02 cm(2) V(-1) s(-1) in excellent agreement with the close pi-stacking and lamellar distances found by structural analysis (0.36 and 1.84 nm, respectively) and absorbs homogenously across the entire visible spectrum as solar cell applications require.

Benzo[1,2-b:4,5-b']bis[b]benzothiophene as solution processible organic semiconductor for field-effect transistors.

Coplanar benzo[1,2-b:4,5-b']bis[b]benzothiophenes (, ) for the application in organic field-effect transistors were synthesized by a simple two-step procedure involving triflic acid induced ring-closure reaction; such solution processed devices show a hole mobility of up to 0.01 cm(2) V(-1) s(-1).

From ambi- to unipolar behavior in discotic dye field-effect transistors.

Ambipolar, solution-processed thin-film transistors based on a discotic dye turn into unipolar behavior after thermal annealing. No evidence for temperature-induced change in injection barrier or interface trapping can be found to explain this phenomenon. Instead, a variation in morphology is considered as the cause for the observed transition from ambipolar to unipolar charge transport.