Substantial photovoltaic response and morphology tuning in benzo[1,2-b:6,5-b′]dithiophene (bBDT) molecular donors

Harschneck, Tobias; Zhou, Nan; Manley, Eric F.; Lou, Sylvia J.; Yu, Xinge; Butler, Melanie R.; Timalsina, Amod; Turrisi, Riccardo; Ratner, Mark A.; Chen, Lin X.; Chang, Robert P. H.; Facchetti, Antonio; Marks, Tobin J.

doi:10.1039/c3cc49620a

Cited by 47 publications

(48 citation statements)

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“…The syntheses of R 2 DTP‐Ph‐NN s are demonstrated in Scheme . Compound 1 and 2 were prepared by literature procedure and 3 obtained by modified procedure with improved yield . Ullman condensation of 3 with 2,3‐bis(hydroxylamino)‐2,3‐dimethylbutane (BHA) yielded 4 .…”

Section: Resultsmentioning

confidence: 99%

Dithienopyrrole Derivatives with Nitronyl Nitroxide Radicals and Their Oxidation to Cationic High‐Spin Molecules

Kolanji

Baumgarten

2020

Chemistry A European J

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Three 1 N‐phenyl nitronyl nitroxide (NN) 4‐substituted dithieno[3,2‐b:2′,3′‐d]pyrrole (DTP) derivatives with R1=4‐phenyl‐, 4H‐, and 4‐methylthiothiophenyl‐ (R12DTP‐Ph‐NN, R1=H, Ph and MeSTh) were designed, synthesized and characterized. The electrochemical properties were studied by cyclic voltammetry (CV). All the molecules exhibited two main oxidation peaks, first for radical cation and next for dication formation. The cation and dication formation were also confirmed by UV/Vis absorption spectroscopy for Ph2DTP‐Ph‐NN and MeSTh2DTP‐Ph‐NN titrated with tris(4‐bromophenyl)aminiumhexachloroantimonate (magic blue). In addition, the cation and dication formation were verified by EPR spectroscopy. Finally, the exchange interactions (J/kB) of NN and radical cation were calculated by DFT studies.

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Section: Resultsmentioning

confidence: 99%

Dithienopyrrole Derivatives with Nitronyl Nitroxide Radicals and Their Oxidation to Cationic High‐Spin Molecules

Kolanji

Baumgarten

2020

Chemistry A European J

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“…Their responses to film processing solvent/additive conditions should help assess processing-morphology generalities for OSC polymers. [51][52][53][54][55] Simple changes in molecular structure [52][53][54] or processing solvent [55] can dramatically affect crystal packing. [47,48] However, while this description is qualitatively correct, depending on the poly mer and processing, crystalline characteristics can vary.…”

Section: Introductionmentioning

confidence: 99%

In Situ Analysis of Solvent and Additive Effects on Film Morphology Evolution in Spin‐Cast Small‐Molecule and Polymer Photovoltaic Materials

Manley

Strzalka

Fauvell

et al. 2018

Advanced Energy Materials

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indicate the realistic possibility of new soft matter technologies. Note that these highperformance laboratory devices are often produced via spin-coating, a reliable fabrication process that enables rapid prototyping and basic research. However, the transition to high throughput film fabrication processes such as blade-coating, roll-to-roll printing, and others will require understanding of film morphology-forming mechanisms operative in spin-coating processes that optimize organic device performance. [13] Traditionally, optimizing device performance relied on empirical screening of spin-casting para meters such as solvent, processing additive, and spin speed, followed by postprocessing analysis of which morphologies are produced by which coating conditions. [14][15][16] For OSC film morphology, grazing incidence wide-angle X-ray scattering (GIWAXS) is especially powerful for monitoring crystallinity, orientation, donor-acceptor intermixing, [14][15][16][17][18] and developing an ex post facto understanding basis for otherwise completely empirical "recipes." While informative, postdeposition analysis can miss important temporal characteristics of film growth processes which can only be identified by in situ techniques. In situ film growth studies utilizing GIWAXS and other techniques during film deposition and drying have been employed by several groups, including our own, to understand crystalline morphology development in organic electronic thin films. [19,20] Characterizing morphology during the film formation process can elucidate important mechanistic pathways and inform rational solution processing parameter optimization.Several recent studies have reported in situ optical and X-ray analyses of organic film growth by roll-to-roll printing, [21] blade To elucidate the details of film morphology/order evolution during spin-coating, solvent and additive effects are systematically investigated for three representative organic solar cell (OSC) active layer materials using combined in situ grazing incidence wide angle x-ray scattering (GIWAXS) and optical reflectance. Two archetypical semiconducting donor (p-type) polymers, P3HT and PTB7, and semiconducting donor small-molecule, p-DTS(FBTTh 2 ) 2 are studied using three neat solvents (chloroform, chlorobenzene, 1,2-dichlorobenzene) and four processing additives (1-chloronaphthalene, diphenyl ether, 1,8-diiodooctane, and 1,6-diiodohexane). In situ GIWAXS identifies several trends: 1) for neat solvents, rapid crystallization occurs that risks kinetically locking the material into multiple crystal structures or crystalline orientations; and 2) for solvent + additive processed films, morphology evolution involves sequential transformations on timescales ranging from seconds to hours, with key divergences dependent on additive/ semiconductor molecular interactions. When π-planes dominate the additive/semiconductor interactions, both polymers and small molecule films follow similar evolutions, completing in 1-5 min. When side chains dominate the additive/semiconductor...

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“…1) (17) and bBDTðTDPPÞ 2 (18). Although previous studies have examined the dynamics of local charge transfer couplings between two sites in great detail (11,12), none has examined the dynamic evolution of the global network topology.…”

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confidence: 99%

Charge transport network dynamics in molecular aggregates

Jackson

Chen

Ratner

2016

Proc. Natl. Acad. Sci. U.S.A.

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Due to the nonperiodic nature of charge transport in disordered systems, generating insight into static charge transport networks, as well as analyzing the network dynamics, can be challenging. Here, we apply time-dependent network analysis to scrutinize the charge transport networks of two representative molecular semiconductors: a rigid n-type molecule, perylenediimide, and a flexible p-type molecule, bBDT(TDPP) 2 . Simulations reveal the relevant timescale for local transfer integral decorrelation to be ∼ 100 fs, which is shown to be faster than that of a crystalline morphology of the same molecule. Using a simple graph metric, global network changes are observed over timescales competitive with charge carrier lifetimes. These insights demonstrate that static charge transport networks are qualitatively inadequate, whereas average networks often overestimate network connectivity. Finally, a simple methodology for tracking dynamic charge transport properties is proposed.organic semiconductors | charge transport | network analysis | dynamic disorder | molecular semiconductors C omputational tools using periodic boundary conditions are integral to understanding charge and excitation transport in crystalline semiconducting materials (1, 2). In noncrystalline systems, where Bloch's theorem is inapplicable and inclusion of structural disorder is required for an accurate description of charge transport, comparable computational strategies are rare. Typically, one uses an approximate solution of the master equation with semiclassical rates derived from a combination of atomistic molecular dynamics (MD) and quantum chemistry. While this strategy has proven effective (3, 4), it possesses obvious deficiencies: it lacks both an explicit inclusion of structural dynamics and an understanding of the topology of charge transport networks.Work in this group and others has proposed a view of charge transport based in network analysis (5-10). Network analysis represents a powerful means of analyzing structurally disordered charge transport networks, with the unique ability to place different mechanisms of charge transport on the same footing via the selection of a suitable graph metric. Recently, network views of charge transport in structurally disordered systems have provided useful insights: notably, the relationship between a molecule's topology and the percolation threshold of its charge transport networks (5, 6), and that charge mobility can be independent of the global morphology, being primarily determined by local molecular packing (7).Although a useful framework, previous applications of network analysis to structurally disordered charge transport networks have neglected the role of dynamic structural disorder: static snapshots of the charge transport network were used for the network analysis. Transport was assumed to occur on a charge transport network defined by time-independent site energies and electronic couplings. Whereas the static picture provides many insights into the nature of charge transport in soft mater...

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Substantial photovoltaic response and morphology tuning in benzo[1,2-b:6,5-b′]dithiophene (bBDT) molecular donors

Cited by 47 publications

References 20 publications

Dithienopyrrole Derivatives with Nitronyl Nitroxide Radicals and Their Oxidation to Cationic High‐Spin Molecules

Dithienopyrrole Derivatives with Nitronyl Nitroxide Radicals and Their Oxidation to Cationic High‐Spin Molecules

In Situ Analysis of Solvent and Additive Effects on Film Morphology Evolution in Spin‐Cast Small‐Molecule and Polymer Photovoltaic Materials

Charge transport network dynamics in molecular aggregates

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