Twisted Crystalline Organic Semiconductor Photodetectors

Jeong, Sehee; Barbosa, Natercia; Tiwari, Akash; Holland, Emma; Huang, Ling-yi; Bhat, Vinayak; Yang, Yuemei; Zhang, Yuze; Whittaker, St. John; Kim, Min‐Woo; Alaei, Aida; Sundaram, Pallavi; Spencer, Rochelle; Brazard, Johanna; Kalyon, Dilhan M.; Risko, Chad; Anthony, John E.; Adachi, Takuji; Shtukenberg, Alexander G.; Kahr, Bart; Lee, Stephanie S.

doi:10.1002/adfm.202212531

Cited by 10 publications

(25 citation statements)

References 88 publications

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“…Wavelength-dependent absorption spectra of twisted organic semiconductor crystals also exhibit band dependencies. Figure a displays POMs and corresponding polarization-angle-dependent absorption spectra for nonbanded and banded TIPS ADT spherulites comprising straight and twisted crystals, respectively . A microspectrophotometer (CRAIC Technologies) mounted on an optical microscope was used to collect localized spectra in the 5 × 5 μm regions highlighted with white squares.…”

Section: Twist-patterned Propertiesmentioning

confidence: 99%

“…In general, P is positively correlated to the crystallization temperaturelower crystallization temperatures (i.e., larger supercoolings that increase the crystallization driving force) promote the growth of finer fibrils that can twist with higher frequency. ,,, P typically reaches a minimum value at some intermediate supercooling, after which further supercooling does not affect P . In TIPS ADT banded spherulites, for example, a minimum P of 10 μm is observed across the range of 20–80 °C .…”

Section: Future Directionsmentioning

confidence: 99%

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Leveling up Organic Semiconductors with Crystal Twisting

Whittaker,

Zhou,

Spencer

et al. 2023

Crystal Growth & Design

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The performance of crystalline organic semiconductors depends on the solid-state structure, especially the orientation of the conjugated components with respect to device platforms. Often, crystals can be engineered by modifying chromophore substituents through synthesis. Meanwhile, dissymetry is necessary for high-tech applications like chiral sensing, optical telecommunications, and data storage. The synthesis of dissymmetric molecules is a labor-intensive exercise that might be undermined because common processing methods offer little control over orientation. Crystal twisting has emerged as a generalizable method for processing organic semiconductors and offers unique advantages, such as patterning of physical and chemical properties and chirality that arises from mesoscale twisting. The precession of crystal orientations can enrich performance because achiral molecules in achiral space groups suddenly become candidates for the aforementioned technologies that require dissymetry.

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Section: Twist-patterned Propertiesmentioning

confidence: 99%

Section: Future Directionsmentioning

confidence: 99%

Leveling up Organic Semiconductors with Crystal Twisting

Whittaker,

Zhou,

Spencer

et al. 2023

Crystal Growth & Design

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“…Modulations of optical and electronic properties are also manifested in banded spherulites. Films of twisted charge transfer complexes 15 and semiconducting molecular crystals demonstrate improved charge mobility 16,17 and photoconductivity 18 . Increased performance is the result of the modulation of crystallographic directions that are exposed to the electrodes or the light source.…”

Section: Introductionmentioning

confidence: 99%

“…Films of twisted charge transfer complexes 15 and semiconducting molecular crystals demonstrate improved charge mobility 16,17 and photoconductivity. 18 Increased performance is the result of the modulation of crystallographic directions that are exposed to the electrodes or the light source. Variation in the crystallization direction normal to the substrate can increase absorption coefficients and/or decrease barriers to charge injection and extraction, resulting in an overall improvement in conductivity and photoconductivity.…”

Section: Introductionmentioning

confidence: 99%

Collimating the growth of twisted crystals of achiral compounds

et al. 2023

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A great proportion of molecular crystals can be made to grow as twisted fibrils. Typically, this requires high crystallization driving forces that lead to spherulitic textures. Here, it is shown how micron size channels fabricated from poly(dimethylsiloxane) (PDMS) serve to collimate the circular polycrystalline growth fronts of optically banded spherulites of twisted crystals of three compounds, coumarin, 2,5-bis(3-dodecyl-2-thienyl)-thiazolo [5,4-d]thiazole, and tetrathiafulvalene. The relationships between helicoidal pitch, growth front coherence, and channel width are measured. As channels spill into open spaces, collimated crystals "diffract" via small angle branching. On the other hand, crystals grown together from separate channels whose bands are out of phase ultimately become a single in-phase bundle of fibrils by a cooperative mechanism yet unknown. The isolation of a single twist sense in individual channels is described. We forecast that such chiral molecular crystalline channels may function as chiral optical wave guides.

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“…As crystals change their orientations systematically, naturally, physical and chemical properties should alternate rhythmically along radii. Indeed, absorptivity, photoluminescence, electrical conductivity, linear dichroism, and linear and circular birefringence , alternate between concentric bands of optical contrast. Here, we investigate whether the morphological evolution of a spherulitic film shows a dependence on the orientation of the underlying structure.…”

Section: Introductionmentioning

confidence: 99%

Self-Patterning Tetrathiafulvalene Crystalline Films

Whittaker,

McDowell,

Bendesky

et al. 2023

Chem. Mater.

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Tetrathiafulvalene (TTF) crystals grown from the melt are organized as spherulites in which helicoidal fibrils growing radially from the nucleation center twist in concert with one another. Alternating bright and dark concentric bands are apparent when films are viewed between crossed polarizers, indicating an alternating pattern of crystallographic faces exposed at the film surface. Band-dependent reorganization of the TTF crystals was observed during exposure to methanol vapor. Crystalline growth appears on bright bands at the expense of the dark bands. After a 24 h period of exposure to methanol vapor, the original spherulites were completely restructured, and the films comprise isolated, concentric circles of crystallites whose orientations are determined by the initial TTF crystal fibril orientation. While the surface of these outgrowths appears faceted and smooth, cross-sectional SEM images revealed a semiporous inner structure, suggesting solventvapor-induced recrystallization. Collectively, these results show that crystal twisting can be used to rhythmically redistribute material. Crystal twisting is a common and often controllable phenomenon independent of molecular or crystal structure and therefore offers a generalizable path to spontaneous pattern formation in a wide range of materials.

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Twisted Crystalline Organic Semiconductor Photodetectors

Cited by 10 publications

References 88 publications

Leveling up Organic Semiconductors with Crystal Twisting

Leveling up Organic Semiconductors with Crystal Twisting

Collimating the growth of twisted crystals of achiral compounds

Self-Patterning Tetrathiafulvalene Crystalline Films

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