Sequencing conjugated polymers by eye

Warr, Daniel; Perdigão, Luı́s M. A.; Pinfold, Harry; Blohm, Jonathan; Stringer, David; Leventis, Anastasia; Bronstein, Hugo; Troisi, Alessandro; Costantini, Giovanni

doi:10.1126/sciadv.aas9543

Cited by 42 publications

(52 citation statements)

References 37 publications

(39 reference statements)

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“…Polymer chain conformations can be predicted theoretically from molecular dynamics simulations, but can also be visualized for polymers adsorbed on surfaces by scanning tunnelling microscopy techniques (Fig. 4e) 85 . In addition, the inherently smaller intrachain bandwidth in D-A copolymers also makes transport less sensitive to conformational disorder 83 .…”

Section: Charge Transport In Low-disorder Conjugated Polymersmentioning

confidence: 99%

Charge transport in high-mobility conjugated polymers and molecular semiconductors

et al. 2020

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Conjugated polymers and molecular semiconductors are emerging as a viable semiconductor technology in industries such as displays, electronics, renewable energy, sensing and healthcare. A key enabling factor has been significant scientific progress in improving their charge transport properties and carrier mobilities, which has been made possible by a better understanding of the molecular structure-property relationships and the underpinning charge transport physics. Here we aim to present a coherent review of how we understand charge transport in these high-mobility van der Waals bonded semiconductors. Specific questions of interest include estimates for intrinsic limits to the carrier mobilities that might ultimately be achievable; a discussion of the coupling between charge and structural dynamics; the importance of molecular conformations and mesoscale structural features; how the transport physics of conjugated polymers and small molecule semiconductors are related; and how the incorporation of counterions in doped films-as used, for example, in bioelectronics and thermoelectric devices-affects the electronic structure and charge transport properties.

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Section: Charge Transport In Low-disorder Conjugated Polymersmentioning

confidence: 99%

Charge transport in high-mobility conjugated polymers and molecular semiconductors

et al. 2020

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“…To safely deposit the SW precursors onto Au(111), we used an electrospray deposition (ESD) device attached to the UHV setup 24,[27][28][29][30][31][32][33] . The spray-deposition was always performed on the Au(111) substrates kept at room temperature and followed by an annealing step at 450 K. As shown in large-scale STM measurements ( Supplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

“…In UHV conditions, the electrospray deposition (ESD) technique allows the introduction of large molecules. Therefore, it is possible to study in UHV conditions the adsorption properties of molecules and their assemblies that mimic established assemblies at the liquid-solid interface 24,[27][28][29][30][31][32][33] . In this context, temperature-dependent STM/AFM investigations of supramolecular systems might enable the analysis of their thermoresponse down to the atomic scale.…”

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confidence: 99%

Giant thermal expansion of a two-dimensional supramolecular network triggered by alkyl chain motion

et al. 2020

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Thermal expansion, the response in shape, area or volume of a solid with heat, is usually large in molecular materials compared to their inorganic counterparts. Resulting from the intrinsic molecule flexibility, conformational changes or variable intermolecular interactions, the exact interplay between these mechanisms is however poorly understood down to the molecular level. Here, we investigate the structural variations of a two-dimensional supramolecular network on Au(111) consisting of shape persistent polyphenylene molecules equipped with peripheral dodecyl chains. By comparing high-resolution scanning probe microscopy and molecular dynamics simulations obtained at 5 and 300 K, we determine the thermal expansion coefficient of the assembly of 980 ± 110 × 10 −6 K −1 , twice larger than other molecular systems hitherto reported in the literature, and two orders of magnitude larger than conventional materials. This giant positive expansion originates from the increased mobility of the dodecyl chains with temperature that determine the intermolecular interactions and the network spacing.

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“…[ 22–24 ] However, the highest electron mobilities demonstrated in these systems so far have only reached somewhat disappointing low values on the order of 0.03 cm 2 V −1 s −1 , [ 20 ] which is significantly lower than what is achievable with other state‐of‐the‐art n‐type polymers. [ 21 ] In this work, we visualize the unique fused backbone structure of these promising rigid‐rod polymers with monomeric precision by state‐of‐the‐art STM imaging [ 25 ] and demonstrate a strategy to optimize their electron transport properties by uniaxial chain alignment. Our aim is to investigate whether these rigid‐rod polymers are capable of exhibiting similarly high electron mobilities as donor–acceptor systems.…”

Section: Figurementioning

confidence: 99%

Anisotropy of Charge Transport in a Uniaxially Aligned Fused Electron‐Deficient Polymer Processed by Solution Shear Coating

et al. 2020

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Precise control of the microstructure in organic semiconductors (OSCs) is essential for developing high‐performance organic electronic devices. Here, a comprehensive charge transport characterization of two recently reported rigid‐rod conjugated polymers that do not contain single bonds in the main chain is reported. It is demonstrated that the molecular design of the polymer makes it possible to achieve an extended linear backbone structure, which can be directly visualized by high‐resolution scanning tunneling microscopy (STM). The rigid structure of the polymers allows the formation of thin films with uniaxially aligned polymer chains by using a simple one‐step solution‐shear/bar coating technique. These aligned films show a high optical anisotropy with a dichroic ratio of up to a factor of 6. Transport measurements performed using top‐gate bottom‐contact field‐effect transistors exhibit a high saturation electron mobility of 0.2 cm2 V−1 s−1 along the alignment direction, which is more than six times higher than the value reported in the previous work. This work demonstrates that this new class of polymers is able to achieve mobility values comparable to state‐of‐the‐art n‐type polymers and identifies an effective processing strategy for this class of rigid‐rod polymer system to optimize their charge transport properties.

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Sequencing conjugated polymers by eye

Abstract: Electrospray deposition and STM as a new analytical technique to sequence conjugated polymers and reveal polymerization defects.

Cited by 42 publications

References 37 publications

Charge transport in high-mobility conjugated polymers and molecular semiconductors

Charge transport in high-mobility conjugated polymers and molecular semiconductors

Giant thermal expansion of a two-dimensional supramolecular network triggered by alkyl chain motion

Anisotropy of Charge Transport in a Uniaxially Aligned Fused Electron‐Deficient Polymer Processed by Solution Shear Coating

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