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Effects of Solvent Vapor Annealing on Morphology and Charge Transport of Poly(3-hexylthiophene) (P3HT) Films Incorporated with Preformed P3HT Nanowires.

ABSTRACT: We systematically studied the influence of solvent vapor annealing on the molecular ordering, morphologies, and charge transport properties of poly(3-hexylthiophene) (P3HT) thin films embedded with preformed crystalline P3HT nanowires (NWs). Solvent vapor annealing (SVA) with chloroform (CF) was found to profoundly impact on the structural and morphological changes, and thus on the charge transport characteristics, of the P3HT-NW-embedded P3HT films. With increased annealing time, the density of crystalline P3HT NWs was increased within the resultant films, and also intra- and intermolecular interactions of the corresponding films were significantly improved. As a result, the P3HT-NW-embedded P3HT films annealed with CF vapor for 20 min resulted in a maximized charge carrier mobility of ~0.102 cm2 V-1 s-1, which is higher than that of pristine P3HT films by 4.4-fold (? = ~0.023 cm2 V-1 s-1).

SUBMITTER: Jang M

PROVIDER: S-EPMC7284567 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

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Effects of Solvent Vapor Annealing on Morphology and Charge Transport of Poly(3-hexylthiophene) (P3HT) Films Incorporated with Preformed P3HT Nanowires.

Jang Mingu M Huh Yang-Il YI Chang Mincheol M

Polymers 20200522 5

We systematically studied the influence of solvent vapor annealing on the molecular ordering, morphologies, and charge transport properties of poly(3-hexylthiophene) (P3HT) thin films embedded with preformed crystalline P3HT nanowires (NWs). Solvent vapor annealing (SVA) with chloroform (CF) was found to profoundly impact on the structural and morphological changes, and thus on the charge transport characteristics, of the P3HT-NW-embedded P3HT films. With increased annealing time, the density of ...[more]

PMID: 32456100

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Project description:During the nanoimprinting lithography (NIL) process, the role of solvent vapor in fabricating the pattern structure and inducing the molecular alignment of nanoimprinted polymer film has been attracting significant attention. We demonstrate here that the molecular orientation and thermal stability of poly(3-hexylthiophene) (P3HT) nanograting film can be affected obviously by the fabricated solvent vapor. A solvent-vapor nanoimprinting lithography (SV-NIL) technique based on a polydimethylsiloxane (PDMS) template is employed to fabricate a P3HT nanograting structure film successfully and solvent vapor is offered by chlorobenzene, chloroform and carbon disulphide, respectively. The molecular orientation of the polymer film is carefully characterized by grazing incidence wide angle X-ray diffraction (GIWAXD) measurements to investigate the effect of various solvent vapors on the molecular orientation of the P3HT nanograting film. For the P3HT nanograting film fabricated by chloroform and chlorobenzene solvent, the edge-on molecular orientation of the typical form II crystallographic structure is induced. However, this indicates that there are both the face-on molecular orientations of the form II and form I crystallographic conformation present for the P3HT nanograting film fabricated by carbon disulphide solvent. Therefore, the fabricated solvent vapor plays a significant role in determining the formation of the molecular orientation of the polymer nanostructure. Then, the role of thermal annealing in the stability of the molecular orientation was investigated for the P3HT nanograting film after a fixed temperature. As for the annealed nanograting film fabricated by chlorobenzene and chloroform solvent vapor, a single edge-on molecular orientation mode of the form I crystallographic structure has been obtained. However, for the annealed nanograting film fabricated by the carbon disulphide solvent, the edge-on and face-on molecular orientations of the form I crystallographic structure are still retained. This indicates that the stability of the form II crystallographic conformation is mainly dependent on the thermal annealing process. Therefore, after the annealing process, the final determining of the molecular alignment and crystallographic conformation depends significantly on the orientation type of the nanograting film before the annealing history, and it can be further inferred that the molecular orientation of the annealed polymer film is still affected by the fabricated solvent vapor significantly. Thus this will provide new understanding and guidance for the research of the topographical structure and molecular alignment of conjugated polymers.

Project description:The self-assembly of ultra-high molecular weight (UHMW) block copolymers (BCPs) remains a complex and time-consuming endeavor owing to the high kinetic penalties associated with long polymer chain entanglement. In this work, we report a unique strategy of overcoming these kinetic barriers through precision solvent annealing of an UHMW polystyrene-block-poly(2-vinylpyridine) BCP system (M w: ∼800 kg/mol) by fast swelling to very high levels of solvent concentration (ϕs). Phase separation on timescales of ∼10 min is demonstrated once a thickness-dependent threshold ϕs value of ∼0.80-0.86 is achieved, resulting in lamellar feature spacings of over 190 nm. The threshold ϕs value was found to be greater for films with higher dry thickness (D 0) values. Tunability of the domain morphology is achieved through controlled variation of both D 0 and ϕs, with the kinetically unstable hexagonal perforated lamellar (HPL) phase observed at ϕs values of ∼0.67 and D 0 values of 59-110 nm. This HPL phase can be controllably induced into an order-order transition to a lamellar morphology upon further increase of ϕs to 0.80 or above. As confirmed by grazing-incidence small-angle X-ray scattering, the lateral ordering of the lamellar domains is shown to improve with increasing ϕs up to a maximum value at which the films transition to a disordered state. Thicker films are shown to possess a higher maximum ϕs value before transitioning to a disordered state. The swelling rate is shown to moderately influence the lateral ordering of the phase-separated structures, while the amount of hold time at a particular value of ϕs does not notably enhance the phase separation process. These large period self-assembled lamellar domains are then employed to facilitate pattern transfer using a liquid-phase infiltration method, followed by plasma etching, generating ordered, high aspect ratio Si nanowall structures with spacings of ∼190 nm and heights of up to ∼500 nm. This work underpins the feasibility of a room-temperature, solvent-based annealing approach for the reliable and scalable fabrication of sub-wavelength nanostructures via BCP lithography.

Dataset Information

Effects of Solvent Vapor Annealing on Morphology and Charge Transport of Poly(3-hexylthiophene) (P3HT) Films Incorporated with Preformed P3HT Nanowires.

Publications

Effects of Solvent Vapor Annealing on Morphology and Charge Transport of Poly(3-hexylthiophene) (P3HT) Films Incorporated with Preformed P3HT Nanowires.

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