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Quantum dot-organic semiconductor hybrid materials are gaining increasing attention as spin mixers for applications ranging from solar harvesting to spin memories. Triplet energy transfer between the inorganic quantum dot (QD) and organic semiconductor is a key step to understand in order to develop these applications. Here we report on the triplet energy transfer from PbS QDs to four energetically and structurally similar tetracene ligands. Even with similar ligands we find that the triplet energy transfer dynamics can vary significantly. For TIPS-tetracene derivatives with carboxylic acid, acetic acid and methanethiol anchoring groups on the short pro-cata side we find that triplet transfer occurs through a stepwise process, mediated via a surface state, whereas for monosubstituted TIPS-tetracene derivative 5-(4-benzoic acid)-12-triisopropylsilylethynyl tetracene (BAT) triplet transfer occurs directly, albeit slower, via a Dexter exchange mechanism. Even though triplet transfer is slower with BAT the overall yield is greater, as determined from upconverted emission using rubrene emitters. This work highlights that the surface-mediated transfer mechanism is plagued with parasitic loss pathways and that materials with direct Dexter-like triplet transfer are preferred for high-efficiency applications. [ABSTRACT FROM AUTHOR]

Acenes are a set of polycyclic aromatic hydrocarbons commonly employed in opto-electronic devices, despite the fact that they can undergo chemical transformation under illumination which is detrimental to device performance. In this study, a series of anthradithiophenes bearing different substituents is investigated, considering the light absorption, concentration dependence, and reactivity with singlet oxygen to understand trends in photostability. Future molecular design can use these results to design more robust materials e.g. for solar conversion, or conversely more photoreactive materials for sensing applications. [ABSTRACT FROM AUTHOR]

Hybrid small-molecule/quantum dot films have the potential to reduce thermalization losses in single-junction photovoltaics as photon multiplication devices. Here grazing incidence X-ray scattering, optical microscopy and IR fluorescence microscopy (probing materials at two distinct wavelengths), provide new insight into highly complex morphologies across nm and μm lengthscales to provide direct links between morphologies and photon multiplication performance. Results show that within the small molecule crystallites three different QD morphologies may be identified; (i) large quantum dot aggregates at the crystallite nucleus, (ii) relatively well-dispersed quantum dots and (iii) as aggregated quantum dots "swept" from the growing crystallite and that regions containing aggregate quantum dot features lead to relatively poor photon multiplication performance. These results establish how combinations of scattering and microscopy may be employed to reveal new insights into the structure and function of small molecule:quantum dot blends. [ABSTRACT FROM AUTHOR]

Derived from the lateral fusion of benzene rings, acenes are a class of π-conjugated molecules containing a single aromatic sextet, where system size is inversely correlated with chemical stability. In the pursuit of creating graphene nanoribbons/nanowires, several extended-ring structures have been synthesized through linear combinations of azaacenes and pyrene. Importantly, these extended systems demonstrate enhanced chemical stability and allow for the construction of macromolecular-sized structures. Here, we present a combined quantum-chemical and experimental study to reveal the cost of these improved characteristics in fully carbon-based systems. The results clearly show that pyrene moieties inserted among acene units do not result in long acene-like structures, rather the pyrene-inserted acene is, electronically, a series of (nearly) isolated acenes. The origin of pyrene's electronic blocking effect and implications on oxidized and photoexcited states of these extended-ring systems are detailed. The results of this investigation definitively show that coupling pyrene in an orthogonal orientation (through the 4, 5/9, 10 positions or e/l faces) to acenes should be eschewed if nanographene-/nanowire-like structures are desired. [ABSTRACT FROM AUTHOR]

Thermal annealing of organic semiconductors is critical for optimization of their electronic properties. The selection of the optimal annealing temperature –often done on a trial-and-error basis– is essential for achieving the most desired micro/nanostructure. While classical materials science relies on time-temperature-transformation (TTT) diagrams to predict such processing-structure relationships, this type of approach is yet to find widespread application in the field of organic electronics. In this work, we constructed a TTT diagram for crystallization of the widely studied organic semiconductor 5,11-bis(triethylsilylethynyl)anthradithiophene (TES-ADT) from its melt. Thermal analysis in the form of isothermal crystallization experiments showed distinctly different types of behaviour depending on the annealing temperature, in agreement with classical crystal nucleation and growth theory. Hence, the TTT diagram correlates with the observed variation in the number of crystal domains, the crystal coverage and film texture as well as the obtained polymorph. As a result, we are able to rationalize the influence of the annealing temperature on the charge-carrier mobility extracted from field-effect transistor (FET) measurements. Evidently, the use of TTT diagrams is a powerful tool to describe structure formation of organic semiconductors and can be used to predict processing protocols that lead to optimal device performance. [ABSTRACT FROM AUTHOR]

Magneto electroluminescence (MEL) is emerging as a powerful tool to study spin dynamics in organic light emitting diodes (OLEDs). The shape of the MEL response is typically used to draw qualitative inference on the dominant process (singlet fission or triplet fusion) in the device. In this study, we develop a quantitative model for MEL and apply it to devices based on rubrene, and three solution processable anthradithiophene emitters. The four emitters allow us to systematically vary the film structure between highly textured, poly-crystalline to amorphous. We find significant diversity in the MEL, with the textured films giving highly structured responses. We find that the additional structure does not coincide with energy anti-crossings, but intersections in the singlet character between adjacent states. In all cases the MEL can be adequately described by an extended Merrifield model. Via the inclusion of charge injection, we are able to draw additional information on underlying physics in OLED devices. [ABSTRACT FROM AUTHOR]

Herein, we report on the fabrication of large-area printed low-voltage organic thin film transistor arrays via minimal-solution bar-coating. We established the bar-coating of the chemically cross-linked polymer dielectric based on poly(4-vinylphenol) and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride by investigating the effects of composition, reaction and printing conditions on film thickness, cross-linking efficacy, and dielectric properties. Subsequently, we elucidated various aspects of large-area (up to 4-inch wafer) bar-coated cross-linked polymeric dielectric prepared from minimal solution (∼100 μL, ∼1.2 μL cm−2) by addressing film uniformity, thickness control, capacitance variation, underlying step coverage, patternability, etc. The resultant polymeric dielectric exhibited good insulating properties as exemplified by a low leakage current density of ∼10−8 A cm−2 (at 1 MV cm−1) and a high areal capacitance of 42.6 nF cm−2. Finally, a highly-crystallized organic semiconductor layer based on 2,8-difluorinated 5,11-bis(triethylsilylethynyl)anthradithiophene was deposited on the bar-coated cross-linked polymeric dielectric via bar-coating, leading to the realization of printed low-voltage organic transistor arrays with minimum ink solution wasted. [ABSTRACT FROM AUTHOR]

The emerging field of electronic textiles is currently hindered by a lack of mechanically robust fibers and yarns that efficiently conduct electricity. Conjugated polymer fibers are promising candidates to meet those requirements. In this work, a wet-spinning process is described to fabricate PEDOT:PSS fibers with electrical conductivities up to 3663 ± 326 S cm−1, Young's moduli up to 22 GPa and tensile strength of 550 MPa, through inclusion of a sulfuric acid drawing step. The mechanism by which the sulfuric acid drawing step enhances the electrical and mechanical properties of the fibers is investigated. Moreover, the electrical conductivity of these fibers was further increased to 4039 ± 215 S cm−1 by immersing the fibers in sulfuric acid for additional time, at the expense, however, of lowering their Young's modulus and tensile strength. Additionally, we demonstrate the use of the fibers in various electronic textile applications such as: (a) flexible textile interconnections in an LED circuit, (b) a proof of concept thermochromic fiber bundle that changes color on demand, (c) a thermoelectric textile device using the fibers as the p-type legs, and (d) using the fibers as the channel in an organic electrochemical transistor to build an LED dimmer. This work presents a unique type of material with the potential of becoming a cornerstone in the emerging field of electronic textiles. [ABSTRACT FROM AUTHOR]

Quantitative singlet fission has been observed for a variety of acene derivatives such as tetracene and pentacene, and efforts to extend the library of singlet fission compounds is of current interest. Preliminary calculations suggest anthradithiophenes exhibit significant exothermicity between the first optically-allowed singlet state, S1, and 2 × T1 with an energy difference of ＞5000 cm−1. Given the fulfillment of this ingredient for singlet fission, here we investigate the singlet fission capability of a difluorinated anthradithiophene dimer (2ADT) covalently linked by a (dimethylsilyl)ethane bridge and derivatized by triisobutylsilylethynyl (TIBS) groups. Photophysical characterization of 2ADT and the single functionalized ADT monomer were carried out in toluene and acetone solution via absorption and fluorescence spectroscopy, and their photo-initiated dynamics were investigated with time-resolved fluorescence (TRF) and transient absorption (TA) spectroscopy. In accordance with computational predictions, two conformers of 2ADT were observed via fluorescence spectroscopy and were assigned to structures with the ADT cores trans or cis to one another about the covalent bridge. The two conformers exhibited markedly different excited state deactivation mechanisms, with the minor trans population being representative of the ADT monomer showing primarily radiative decay, while the dominant cis population underwent relaxation into an excimer geometry before internally converting to the ground state. The excimer formation kinetics were found to be solvent dependent, yielding time constants of ∼1.75 ns in toluene, and ∼600 ps in acetone. While the difference in rates elicits a role for the solvent in stabilizing the excimer structure, the rate is still decidedly long compared to most singlet fission rates of analogous dimers, suggesting that the excimer is neither a kinetic nor a thermodynamic trap, yet singlet fission was still not observed. The result highlights the sensitivity of the electronic coupling element between the singlet and correlated triplet pair states, to the dimer conformation in dictating singlet fission efficiency even when the energetic requirements are met. [ABSTRACT FROM AUTHOR]

A unified patterning and annealing approach was successfully demonstrated for 5,11-bis(triethylsilylethynyl)-anthradithiophene (TES-ADT) films spun-cast on polymer-treated SiO2 dielectrics. First, rubbery polydimethylsiloxane (μ-PDMS) stamps with microscale periodic grooves were swollen in 1,2-dichloroethane and then softly placed onto amorphous-like TES-ADT films. In this case, the film sides physically in contact with the wet stamps were quickly absorbed into the PDMS matrix while the non-contact area formed highly-ordered phases by the solvent-annealing effect. The resulting patterns of TES-ADT contained discernable crystallites, where the grain sizes drastically decreased and their shapes transformed from spherulites to optically featureless ones with a decreasing line width from 100 to 2.5 μm. Unlike ordinary systems containing spherulitic domains, the 2.5 μm line-confined TES-ADT patterns contained layer-stacked crystallites but an optically invisible grain boundary, yielding an unexpectedly high field-effect mobility of 2.60 cm2 V−1 s−1 in organic field-effect transistors (OFETs), with narrow deviations less than 8% (averaged from 42 devices). The results suggest that the well π-overlapped grains and their smooth connections are key factors to achieve high performance multi-array OFET applications. [ABSTRACT FROM AUTHOR]

Anthradithiophenes (ADTs) are typically synthesized as inseparable mixtures of regioisomers. In this paper, we describe the synthesis of desymmetrized anthradithiophenes containing one trialkylsilylethyne solubilizing group, which allowed chromatographic separation of the three resulting isomers. Cyclic voltammograms, as well as absorption and emission spectra for all isomers, were nearly identical. However, X-ray crystallography revealed that the positions of the sulfur atoms in each isomer strongly influence crystal packing, corroborating calculations that show the S–π interaction to be less stabilizing than the C–H–π interaction. Isomer 3c packs in a pseudo 1-D fashion while isomers 3a and 3b pack as isolated π-stacked pairs. Isomer 3c shows a field-effect mobility four orders of magnitude higher than isomers 3a and 3b, presumably due to this difference in packing motif. [ABSTRACT FROM AUTHOR]

Spin-coating is currently the most widely used solution processing method in organic electronics. Here, we report, for the first time, a direct investigation of the formation process of the small-molecule organic semiconductor (OSC) 6,13-bis(triisopropylsilylethynyl) (TIPS)-pentacene during spin-coating in the context of an organic thin film transistor (OTFT) application. The solution thinning and thin film formation were monitored in situ by optical reflectometry and grazing incidence wide angle X-ray scattering, respectively, both of which were performed during spin-coating. We find that OSC thin film formation is akin to a quenching process, marked by a deposition rate of ∼100 nm s−1, nearly three orders of magnitude faster than drop-casting. This is then followed by a more gradual crystallization and healing step which depends upon the spinning speed. We associate this to further crystallization and healing of defects by residency of the residual solvent trapped inside the kinetically trapped film. The residency time of the trapped solvent is extended to several seconds by slowing the rotational speed of the substrate and is credited with improving the carrier mobility by nearly two orders of magnitude. Based on this insight, we deliberately slow down the solvent evaporation further and increase the carrier mobility by an additional order of magnitude. These results demonstrate how spin-coating conditions can be used as a handle over the crystallinity of organic semiconductors otherwise quenched during initial formation only to recrystallize and heal during extended interaction with the trapped solvent. [ABSTRACT FROM AUTHOR]

6,13-Bis(triisopropylsilylethynyl) (TIPS)-pentacene has proven to be a promising soluble p-type material for organic thin film transistors as well as for photovoltaics. In this work, we show that adding electron-withdrawing nitrile functional groups to TIPS-pentacene turns it into an n-type material, which can be used as an acceptor for organic solar cells. Several new cyanopentacenes with different trialkylsilyl functional groups have been synthesized. The HOMO–LUMO energy levels can be tuned by varying the number of nitrile groups, while the trialkylsilyl groups control crystal packing and film morphology. Solar cells were fabricated from a blend of poly(3-hexylthiophene) (P3HT) as the donor and the cyanopentacenes as acceptors, and we found that the acceptors that stack in a 1D “sandwich-herringbone” exhibited the best performance of derivatives in this study. A solar cell fabricated from a blend of P3HT and 2,3-dicyano-6,13-bis-(tricyclopentylsilylethynyl)pentacene (2,3-CN2-TCPS-Pn) exhibited a power conversion efficiency of 0.43% under 100 mW cm−2AM 1.5 illumination. [ABSTRACT FROM AUTHOR]

Correction for 'Large-area printed low-voltage organic thin film transistors via minimal-solution bar-coating' by Sujin Sung et al., J. Mater. Chem. C, 2020, 8, 15112–15118, DOI: 10.1039/D0TC03089A. [ABSTRACT FROM AUTHOR]

Photoinduced electron transfer into mesoporous oxide substrates is well-known to occur efficiently for both singlet and triplet excited states in conventional metal-to-ligand charge transfer (MLCT) dyes. However, in all-organic dyes that have the potential for producing two triplet states from one absorbed photon, called singlet fission dyes, the dynamics of electron injection from singlet vs. triplet excited states has not been elucidated. Using applied bias transient absorption spectroscopy with an anthradithiophene-based chromophore ( ADT-COOH ) adsorbed to mesoporous indium tin oxide ( nanoITO ), we modulate the driving force and observe changes in electron injection dynamics. ADT-COOH is known to undergo fast triplet pair formation in solid-state films. We find that the electronic coupling at the interface is roughly one order of magnitude weaker for triplet vs. singlet electron injection, which is potentially related to the highly localized nature of triplets without significant charge-transfer character. Through the use of applied bias on nanoITO : ADT-COOH films, we map the electron injection rate constant dependence on driving force, finding negligible injection from triplets at zero bias due to competing recombination channels. However, at driving forces greater than -0.6 eV, electron injection from the triplet accelerates and clearly produces a trend with increased applied bias that matches predictions from Marcus theory with a metallic acceptor., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We show that the method we have developed for measuring the singlet exciton diffusion length in blends with [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) can be applied not only to polymeric materials, but also to small molecule organic semiconductors. Small organic molecules have a large potential for molecular re-organization upon thermal annealing. Here we show that the exciton diffusion length is decreased upon annealing from 9 to 3 nm in a thin film of a diketopyrrolopyrrole derivative. Such a variation is attributed to exciton delocalization effects in the crystalline domains that are formed during the annealing process as well as to the exciton quenching at grain boundaries.

Acenes larger than pentacene are predicted to possess enticing electronic properties, but are insoluble and prone to rapid decomposition. Utilizing a combination of functionalization strategies, we present stable, solution-processable hexacenes and an evaluation of their hole and electron transport properties.

Amide functionalized anthradithiophenes (ADTs) play active acceptor roles in polymer bulk-heterojunction solar cells. The first separation of ADT isomers is reported, and the regiochemistry of the ADT has significant impact on crystal packing and solar cell performance. Cell efficiency up to 0.80%, due in large part to high open-circuit voltage (V(OC) > 1.0 V), is achieved in bulk-heterojunction solar cells comprising syn-ADT and poly(3-hexylthiophene).

Functionalization of the pro-cata positions of pentacene with groups held perpendicular to the aromatic plane, in this case through a rigid 1,3-dioxole unit, yields pentacene derivatives that are stable and soluble, and still maintain edge-to-face interactions in the solid state.