Crystallization and Melting Behavior of Poly(3-butylthiophene), Poly(3-octylthiophene), and Poly(3-dodecylthiophene)

Causin, Valerio; Marega, Carla; Marigo, Antonio; Valentini, Luca; Kenny, J. M.

doi:10.1021/ma048159+

Cited by 157 publications

(184 citation statements)

References 34 publications

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“…Along the same line, Causin et al reported that P3DDT is crystallizing faster than poly(3-butylthiophene) because of the increased molecular mobility in the melt as the side-chain length increases. 48 This explains also the observation of a lower overall crystallinity in as spin-coated layers of P3ATs for shorter side chains. This limited molecular mobility may also account for the lower crystallinity in as spin-coated P3AT films with the shortest side chains.…”

Section: Methodsmentioning

confidence: 78%

Impact of Thermal Annealing on the Semicrystalline Nanomorphology of Spin-Coated Thin Films of Regioregular Poly(3-alkylthiophene)s as Observed by High-Resolution Transmission Electron Microscopy and Grazing Incidence X-ray Diffraction

et al. 2012

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The impact of thermal annealing on the growth of crystalline nanodomains of poly(3-alkylthiophene) (P3AT) in thin films (15−20 nm thick) was investigated as a function of length of alkyl side chain by combined low-dose highresolution transmission electron microscopy (HR-TEM) and grazing incidence X-ray diffraction (GIXD). Statistical analysis of the data yields the characteristic dimensions of the face-on oriented P3AT nanocrystals, i.e., average stem length l c along backbones and lateral dimension perpendicular to the stems l a along side chains. The following trends were identified: (i) in as-spin-coated films, the proportion of face-on oriented nanocrystals increases with the number of carbon atoms in the side chain, (ii) annealing favors the lateral in-plane growth of the nanocrystals along the side chain direction (a P3AT axis), (iii) for a given P3AT, the proportion of face-on oriented domains increases with annealing temperature, (iv) lateral growth along the a P3AT axis is most efficient for the longer octyl side chains, and (v) thermal annealing induces only modest lamellar thickening which is limited by the poor slide diffusion of π-stacked P3AT chains as opposed to lateral growth favored by weak van der Waals interactions between layers of n-alkyl side chains. The increase in the population of face-on oriented crystallites, observed when the length of the side chain increases, coincides with a corresponding decrease in the field effect mobility in annealed P3AT thin films.

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Section: Methodsmentioning

confidence: 78%

Impact of Thermal Annealing on the Semicrystalline Nanomorphology of Spin-Coated Thin Films of Regioregular Poly(3-alkylthiophene)s as Observed by High-Resolution Transmission Electron Microscopy and Grazing Incidence X-ray Diffraction

et al. 2012

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“…With regards to these observations, the relative crystallinities of the terpolymers were compared quantitatively by estimating their heat of crystallization (∆Hc). [57][58][59] The ∆Hc values of the terpolymers increased remarkably from 5.8 (P1) to 16.2 J/g (P5) with increasing Se content, indicating a remarkable increase in the crystallinity. These significant differences in the crystalline behaviors of the terpolymers could affect their electrical properties (i.e., charge mobility) as well as their solubility in the solvent and their miscibility with fullerene acceptors.…”

Section: Resultsmentioning

confidence: 97%

Determining Optimal Crystallinity of Diketopyrrolopyrrole-Based Terpolymers for Highly Efficient Polymer Solar Cells and Transistors

et al. 2014

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A new series of conjugated random terpolymers (PDPP2T-Se-Th) was synthesized from electron-deficient diketopyrrolopyrrole (DPP) based unit in conjugation with two electronrich selenophene (Se) and thiophene (Th) species, with a view to inducing different crystalline behaviors of the polymers. The crystallinity of the polymers can be systematically controlled by tuning the ratio between Se and Th; an increase in Se content induced a remarkable increase in the melting and crystallization temperatures as well as the crystallinity of the PDPP2T-Se-Th terpolymers. These changes in the crystalline properties of polymers had a dramatic effect on the performances of organic field-effect transistors (OFETs) and polymer solar cells (PSCs). However, their effect on each type of devices was very different.The charge carrier mobilities of the PDPP2T-Se-Th terpolymers in OFET devices increased remarkably as the Se content increased in the polymers, showing that PDPP2T-Se100 with Se/Th ratio= 100/0 had very high hole and electron mobilities (4.72 and 5.54 cm 2 V -1 s -1 , respectively) with well-balanced ambipolar property. In contrast, the best power conversion efficiency (PCE) of 7.2% was observed for the PDPP2T-Se10-Th90 polymers that had Se/Th ratio of 10/90 due to the synergistic contributions from high charge mobility and optimized bulk-heterojunction (BHJ) morphology with fullerene acceptors. Therefore, the Se units in the polymer backbone could serve to (1) enhance charge carrier mobility and (2) optimize BHJ morphology, both of which affect the performance of the PSCs. To understand the effects of the crystallinity of random terpolymers on their performances in OTFTs and PSCs, we systematically investigated the effects of the Se/Th compositions on their optical, electrical, and structural properties.

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“…Moderate crystallinity is usually observed when P3HT films are subjected to isothermal crystallization after melting, presumably because of the limited mobility of polymer chains in the rigid amorphous phase. 61 A number of groups have investigated the growth and crystallization of P3HT from solution. The motivation of these studies was to decouple the crystallization mechanism, which should be slow for improved crystal perfection, from the rather fast thin film processing as in the case of spin coating.…”

Section: Controlling Nucleation and Growthmentioning

confidence: 99%

Structure and morphology control in thin films of regioregular poly(3‐hexylthiophene)

Brinkmann

2011

J Polym Sci B Polym Phys

358

388

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This review focuses on the structural control in thin films of regioregular poly(3-hexylthiophene) (P3HT), a workhorse among conjugated semiconducting polymers. It highlights the correlation existing between processing conditions and the resulting structures formed in thin films and in solution. Particular emphasis is put on the control of nucleation, crystallinity and orientation. P3HT can generate a large palette of morphologies in thin films including crystalline nanofibrils, spherulites, interconnected semicrystalline morphologies and nanostructured fibers, depending on the elaboration method and on the macromolecular parameters of the polymer. Effective means developed in the recent literature to control orientation of crystalline domains in thin films, especially by using epitaxial crystallization and controlled nucleation conditions are emphasized.

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Crystallization and Melting Behavior of Poly(3-butylthiophene), Poly(3-octylthiophene), and Poly(3-dodecylthiophene)

Cited by 157 publications

References 34 publications

Impact of Thermal Annealing on the Semicrystalline Nanomorphology of Spin-Coated Thin Films of Regioregular Poly(3-alkylthiophene)s as Observed by High-Resolution Transmission Electron Microscopy and Grazing Incidence X-ray Diffraction

Impact of Thermal Annealing on the Semicrystalline Nanomorphology of Spin-Coated Thin Films of Regioregular Poly(3-alkylthiophene)s as Observed by High-Resolution Transmission Electron Microscopy and Grazing Incidence X-ray Diffraction

Determining Optimal Crystallinity of Diketopyrrolopyrrole-Based Terpolymers for Highly Efficient Polymer Solar Cells and Transistors

Structure and morphology control in thin films of regioregular poly(3‐hexylthiophene)

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