Tuning Polythiophene Crystallization through Systematic Side Chain Functionalization

Ho, Victor; Boudouris, Bryan W.; Segalman, Rachel A.

doi:10.1021/ma101697m

Cited by 152 publications

(254 citation statements)

References 58 publications

Supporting

Mentioning

214

Contrasting

Unclassified

Order By: Relevance

“…This observation is in line with prior reports, which show that increasing the length of the side alkyl chain to more than six carbon atoms deteriorates crystallinity and photovoltaic performance. 38,39 The higher molecular level ordering of our alkylthiophene copolymers is consistent with the reports of enhanced mobility and device performance. 40,41 This further signifies the importance of characterising the molecular level ordering and crystallinity of copolymer films, which could be altered during various processing methods, and may be responsible for the extent of exciton diffusion.…”

Section: Exciton Diffusion and Structural Measurements Of P3ht-co-p3ddtsupporting

confidence: 89%

Tuning crystalline ordering by annealing and additives to study its effect on exciton diffusion in a polyalkylthiophene copolymer

Chowdhury

Sajjad

Savikhin

et al. 2017

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

aThe influence of various processing conditions on the singlet exciton diffusion is explored in films of a conjugated random copolymer poly-(3-hexylthiophene-co-3-dodecylthiophene) (P3HT-co-P3DDT) and correlated with the degree of crystallinity probed by grazing incidence X-ray scattering and with exciton bandwidth determined from absorption spectra. The exciton diffusion coefficient is deduced from exciton-exciton annihilation measurements and is found to increase by more than a factor of three when thin films are annealed using CS 2 solvent vapour. A doubling of exciton diffusion coefficient is observed upon melt annealing at 200 1C and the corresponding films show about 50% enhancement in the degree of crystallinity. In contrast, films fabricated from polymer solutions containing a small amount of either solvent additive or nucleating agent show a decrease in exciton diffusion coefficient possibly due to formation of traps for excitons. Our results suggest that the enhancement of exciton diffusivity occurs because of increased crystallinity of alkyl-stacking and longer conjugation of aggregated chains which reduces the exciton bandwidth.

show abstract

Section: Exciton Diffusion and Structural Measurements Of P3ht-co-p3ddtsupporting

confidence: 89%

Tuning crystalline ordering by annealing and additives to study its effect on exciton diffusion in a polyalkylthiophene copolymer

Chowdhury

Sajjad

Savikhin

et al. 2017

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…It also demonstrated that increasing side chain length increases the melting temperature of these polymers, in agreement with experiments performed in Ref. [59]. The ability to systematically vary side chain length and attraction strength without side effects was the key advantage in these exploratory simulations over atomistically-detailed models.…”

Section: Large-scale Morphology Predictionssupporting

confidence: 85%

Computationally connecting organic photovoltaic performance to atomistic arrangements and bulk morphology

Jones

Jankowski

2017

Molecular Simulation

View full text Add to dashboard Cite

Rationally designing roll-to-roll printed organic photovoltaics requires a fundamental understanding of active layer morphologies optimized for charge separation and transport, and which ingredients can be used to self-assemble those morphologies. In this review article we discuss advances in three areas of computational modeling that provide insight into active layer morphology and the charge transport properties that result. We explain the computational bottlenecks prohibiting atomistically-detailed simulations of device-scale active layers and the coarse-graining and hardware acceleration strategies for overcoming them. We review coarse-grained simulations of organic photovoltaic active layers and show that high throughput simulations of experimentally-relevant length scales are now accessible. We describe a new Python package diffractometer that permits grazing-incidence X-ray scattering patterns of simulated active layers to be compared against experiments. We explain the accurate calculation of charge-carrier mobilities from coarse-grained active layer morphologies by using atomistic backmapping, quantum chemical calculations, and kinetic Monte Carlo simulations. We employ these simulations to show that ordering of poly(3-hexylthiophene-2,5-diyl) explains a factor of 1000 improvement in charge mobility. In concert, we present a suite of computational tools enabling large-scale electronic properties of organic photovoltaics to be studied and screened for by molecular simulations.

show abstract

“…This effect is due to the intercalation of PCBM (5) in PT2T (4) (Figure 9), embrittling the blend and hindering the formation of independent crystalline domains of PT2T (4) and PCBM (5) for efficient charge transport. 83 This effect is also seen with larger spacing, such as PBTTT (6), 69,94,95 and PQT (7). 89 It is important to note that this is dependent on the side chains as well; long, branching side chains can block intercalation in PBTTT (6), limiting these effects.…”

Section: Effect Of Alkyl Side Chainsmentioning

confidence: 90%

“…53 Side chain branching is another powerful tool that disrupts crystallinity to a greater extent than linear chains, with minimal effects on the morphology. 83,84 For example, poly(3-(2'-ethyl)hexylthiophene) (P3EHT) was investigated and compared against P3HT (2b) and poly(3-dodecylthiophene) (P3DDT). P3EHT had significantly lower melting temperature (T m ) and charge carrier mobility compared with P3HT (2b) and P3DDT, implying that the use of branching side chains may provide even more significant effects in lowering modulus, though at the cost of charge mobility.…”

Section: Effect Of Alkyl Side Chainsmentioning

confidence: 99%

“…P3EHT had significantly lower melting temperature (T m ) and charge carrier mobility compared with P3HT (2b) and P3DDT, implying that the use of branching side chains may provide even more significant effects in lowering modulus, though at the cost of charge mobility. 83 The effect of the alkyl side chain on the mechanical properties in P3AT (2) seems to be largely dependent on T g changes, as well as a decrease in percentage of carbon atoms along the main chain backbone and can be controlled by rational design. 51 In most cases, the decrease in T g is also accompanied by decreases in the device efficiency, an effect which leads to the aforementioned belief that mechanical properties and efficiency are directly connected.…”

Section: Effect Of Alkyl Side Chainsmentioning

confidence: 99%

See 1 more Smart Citation

Structure and design of polymers for durable, stretchable organic electronics

Onorato

Pakhnyuk

Luscombe

2016

Polym J

View full text Add to dashboard Cite

The field of stretchable electronics has recently gained significant interest from the academic community, with a focus on producing materials that demonstrate reliable electrical performance with improved response to mechanical deformation. This review highlights the recent progress in understanding the relationships between the mechanical behavior and electrical performance of such devices. Potential solutions can take the form of intrinsically elastic polymers, polymer semiconductor/ elastomer blends and alternative engineering-oriented approaches, which are discussed herein. Trends and design strategies are beginning to manifest in this early stage of the stretchable electronics field. The development of stretchable electrical systems can provide unique applications of organic electronics.

show abstract

Tuning Polythiophene Crystallization through Systematic Side Chain Functionalization

Cited by 152 publications

References 58 publications

Tuning crystalline ordering by annealing and additives to study its effect on exciton diffusion in a polyalkylthiophene copolymer

Tuning crystalline ordering by annealing and additives to study its effect on exciton diffusion in a polyalkylthiophene copolymer

Computationally connecting organic photovoltaic performance to atomistic arrangements and bulk morphology

Structure and design of polymers for durable, stretchable organic electronics

Contact Info

Product

Resources

About