Isomerically Pure <i>syn</i>-Anthradithiophenes: Synthesis, Properties, and FET Performance

Lehnherr, Dan; Waterloo, Andreas R.; Goetz, Katelyn P.; Payne, Marcia M.; Hampel, Frank; Anthony, John E.; Jurchescu, Oana D.; Tykwinski, Rik R.

doi:10.1021/ol301503k

Cited by 80 publications

(72 citation statements)

References 29 publications

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“…[18, 34–36] We thus employed our vibration-assisted crystallization (VAC) method, in which the semiconductor solution is perturbed with gentle vibrations applied during film growth in a direction perpendicular to the substrate. [12] In an earlier report, we showed that this procedure yields lower trap densities and enhanced device performance by promoting molecular assembly in a lowest-potential energy configuration.…”

Section: Resultsmentioning

confidence: 99%

The Influence of Isomer Purity on Trap States and Performance of Organic Thin‐Film Transistors

Diemer

Hayes

Welchman

et al. 2016

Adv Elect Materials

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Organic field-effect transistor (OFET) performance is dictated by its composition and geometry, as well as the quality of the organic semiconductor (OSC) film, which strongly depends on purity and microstructure. When present, impurities and defects give rise to trap states in the bandgap of the OSC, lowering device performance. Here, 2,8-difluoro-5,11-bis(triethylsilylethynyl)-anthradithiophene is used as a model system to study the mechanism responsible for performance degradation in OFETs due to isomer coexistence. The density of trapping states is evaluated through temperature dependent current-voltage measurements, and it is discovered that OFETs containing a mixture of syn- and anti-isomers exhibit a discrete trapping state detected as a peak located at ~ 0.4 eV above the valence-band edge, which is absent in the samples fabricated on single-isomer films. Ultraviolet photoelectron spectroscopy measurements and density functional theory calculations do not point to a significant difference in electronic band structure between individual isomers. Instead, it is proposed that the dipole moment of the syn-isomer present in the host crystal of the anti-isomer locally polarizes the neighboring molecules, inducing energetic disorder. The isomers can be separated by applying gentle mechanical vibrations during film crystallization, as confirmed by the suppression of the peak and improvement in device performance.

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Section: Resultsmentioning

confidence: 99%

The Influence of Isomer Purity on Trap States and Performance of Organic Thin‐Film Transistors

Diemer

Hayes

Welchman

et al. 2016

Adv Elect Materials

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“…From a materials design standpoint, it is important to realize that the substitution of thiophene into an acene structure can lead to an isomeric mixture of products. 146,[148][149][150] In addition to isomeric purity, molecular symmetry can play a role. For molecules with low degrees of symmetry, adjacent molecules can pack in a disordered manner despite the molecules being isomerically equivalent.…”

Section: Azapentacenes and Benzodithiophene As Model Systems To Invesmentioning

confidence: 99%

“…These results can be related back to the characteristics of isomerically pure ADT molecular materials. Analysis of the ADT crystal structures 146,[148][149][150] shows that the dominant disordermers tend to minimize sulfur contacts among nearest neighbors: The anti ADT isomer is able to sustain a pattern of minimal sulfur contacts in the solid state, while the symmetry of the syn ADT isomer does not allow this to occur, resulting in the presence of much more disorder in the crystal; the larger degree of disorder in syn ADT appears to be the reason behind the worse transistor performance when compared to transistors using anti ADT as the active layer. Thus, while heteroatoms are widely used in the design of organic semiconductors, making seemingly subtle changes in the chemistry of the π-conjugated backbone through heteroatom substitution to alter the redox and (opto)electronic characteristics, can have wide ranging materials implications.…”

Section: Azapentacenes and Benzodithiophene As Model Systems To Invesmentioning

confidence: 99%

Noncovalent Interactions in Organic Electronic Materials

Ravva

Risko

Brédas

2017

Non-Covalent Interactions in Quantum Chemistry and Physics

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In this Chapter, we provide an overview of how noncovalent interactions, determined by the chemical structure of π-conjugated molecules and polymers, govern essential aspects of the electronic, optical, and mechanical characteristics of organic semiconductors. We begin by describing general aspects of materials design, including the wide variety of chemistries exploited to control the electronic and optical properties of these materials. We then discuss explicit examples of how the study of noncovalent interactions can provide deeper chemical insights that can improve the design of new generations of organic electronic materials.2

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“…[45] Different modifications of the silylethyne-functionalized acenes have subsequently been used to fine-tune crystal packing and enhance electrical properties. [46][47][48][49][50] In parallel, this synthetic platform has been extended to produce an entire set of acene and hetero-acene p-type semiconductors with varying substituent groups, [24,38,[51][52][53][54][55] for example the fluorinated triethylsilylethynyl-substituted anthradithiophene (diF-TES ADT), [24,56] triethylgermylethynyl-substituted anthradithiophene (diF-TEG ADT), [57] and difluoro-(tri-sec-butylsilyl ethynyl) anthradithiophene (diF-TSBS ADT). [55,58] The nature and size of the substituent group affects both the film texture and the crystalline packing of the semiconductor and therefore alters the performance of the material.…”

Section: P-type Small Molecule Organic Semiconductorsmentioning

confidence: 99%

Versatile Organic Transistors by Solution Processing

2015

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A selection of the latest developments in organic electronic materials and organic field-effect transistor (OFET) devices is reviewed here with an emphasis on the synthetic and manufacturing versatility, ease of processing, and low cost offered by solution processability. At the heart of these benefits is the nature of the weak van der Waals intermolecular interactions inherent to organic compounds. This allows processability with a relatively small amount of energy investment. Material solubility, in particular, creates unique pathways for film fabrication and the design of new device architectures, while presenting new manufacturing challenges to explore. In this review we provide a chronological presentation of the important developments in the solution-deposited organic small-molecule semiconductor, dielectric, and electrode materials used in OFETs, making specific note of current benchmarks. Organic device architectures and fabrication methods that are characterized by reduced complexity and ease of implementation are discussed.

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Isomerically Pure syn-Anthradithiophenes: Synthesis, Properties, and FET Performance

Cited by 80 publications

References 29 publications

The Influence of Isomer Purity on Trap States and Performance of Organic Thin‐Film Transistors

The Influence of Isomer Purity on Trap States and Performance of Organic Thin‐Film Transistors

Noncovalent Interactions in Organic Electronic Materials

Versatile Organic Transistors by Solution Processing

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