Controlling polymer chain alignment through processing is a means of tuning the charge transport of solution‐based conjugated polymers. In this work, a processing strategy is proposed in which an external electric field (E‐field) is applied to the coating blade (E‐blade) to align polymer chain during solution‐shearing, a meniscus‐guided coating technique. A theoretical model based on dielectrophoresis quantitatively describes and predicts the alignment process and is used to guide the selection of the optimal conditions of the applied E‐field. Using these conditions, more than twofold increase in chain alignment is observed for E‐bladed thin films of a diketopyrrolopyrrole (DPP) semiconducting polymer without affecting other morphological aspects such as film thickness, film coverage, or fiber‐like aggregation. Organic field effect transistors based on the E‐bladed DPP polymer are fabricated at ambient conditions and over areas of a few cm2. They display a threefold improvement in their mobilities and a strong enhancement in charge transport anisotropy compared to films prepared without E‐field. These results reveal a synergistic alignment effect from both the solution‐shearing process and the applied E‐field, and introduce a novel and general approach to control the morphology and the electrical properties of solution‐coated conjugated polymer thin films.
- NSF-PAR ID:
- 10252953
- Date Published:
- Journal Name:
- Journal of Materials Chemistry C
- Volume:
- 8
- Issue:
- 43
- ISSN:
- 2050-7526
- Page Range / eLocation ID:
- 15086 to 15091
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
more » « less
Metal oxide (MO) semiconductor thin films prepared from solution typically require multiple hours of thermal annealing to achieve optimal lattice densification, efficient charge transport, and stable device operation, presenting a major barrier to roll-to-roll manufacturing. Here, we report a highly efficient, cofuel-assisted scalable combustion blade-coating (CBC) process for MO film growth, which involves introducing both a fluorinated fuel and a preannealing step to remove deleterious organic contaminants and promote complete combustion. Ultrafast reaction and metal–oxygen–metal (M-O-M) lattice condensation then occur within 10–60 s at 200–350 °C for representative MO semiconductor [indium oxide (In2O3), indium-zinc oxide (IZO), indium-gallium-zinc oxide (IGZO)] and dielectric [aluminum oxide (Al2O3)] films. Thus, wafer-scale CBC fabrication of IGZO-Al2O3thin-film transistors (TFTs) (60-s annealing) with field-effect mobilities as high as ∼25 cm2V−1s−1and negligible threshold voltage deterioration in a demanding 4,000-s bias stress test are realized. Combined with polymer dielectrics, the CBC-derived IGZO TFTs on polyimide substrates exhibit high flexibility when bent to a 3-mm radius, with performance bending stability over 1,000 cycles.
-
more » « less
Abstract Highly crystalline thin films in organic semiconductors are important for applications in high‐performance organic optoelectronics. Here, the effect of grain boundaries on the Hall effect and charge transport properties of organic transistors based on two exemplary benchmark systems is elucidated: (1) solution‐processed blends of 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene (C8‐BTBT) small molecule and indacenodithiophene‐benzothiadiazole (C16IDT‐BT) conjugated polymer, and (2) large‐area vacuum evaporated polycrystalline thin films of rubrene (C42H28). It is discovered that, despite the high field‐effect mobilities of up to 6 cm2V−1s−1and the evidence of a delocalized band‐like charge transport, the Hall effect in polycrystalline organic transistors is systematically and significantly underdeveloped, with the carrier coherence factor α < 1 (i.e., yields an underestimated Hall mobility and an overestimated carrier density). A model based on capacitively charged grain boundaries explaining this unusual behavior is described. This work significantly advances the understanding of magneto‐transport properties of organic semiconductor thin films.
-
more » « less
Abstract A high performance diketopyrrolopyrrole (DPP)–based semiconducting polymer is modified with ligands to enable metal coordination, and its subsequent effect as field‐effect transistors is investigated. In specific, pyridine‐2,6‐dicarboxamide (PDCA) units are incorporated in a DPP–based polymer backbone with a content from 0 to 30 mol%, and the resulting polymers are then mixed with Fe(II) ions. The coordination and spontaneous oxidation converts Fe(II) to Fe(III) ions to result in Fe(III)‐containing metallopolymers. The resulting metallopolymers are observed to show good solubility in organic solvents and can be easily processed as thin films. The charge transport characteristics are subsequently investigated through the fabrication of field–effect transistor devices, in which an enhanced charge carrier mobility with the Fe(III)‐containing metallopolymers is observed. In specific, an almost twofold improvement in the charge carrier mobility is obtained for the 20% PDCA‐containing polymer after Fe coordination (from 0.96 to 1.84 cm2V−1s−1). Furthermore, the operation stability of the metallopolymer‐based devices is found to be significantly improved with low bias stress. Its superior electrical characteristics are attributed to the doping effect of the Fe ions. This study indicates that incorporation of appropriate metallic ions to polymer presents a viable approach to enhance the performance of polymer–based transistor devices.
-
more » « less
Cyclic voltammetry was applied to investigate the permselective properties of electrode-supported ion-exchange polymer films intended for use in future molecular-scale spectroscopic studies of bipolar membranes. The ability of thin ionomer film assemblies to exclude mobile ions charged similarly to the polymer (co-ions) and accumulate ions charged opposite to the polymer (counterions) was scrutinized through use of the diffusible redox probe molecules [Ru(NH3)6]3+and [IrCl6]2−. With the anion exchange membrane (AEM) phase supported on a carbon disk electrode, bipolar junctions formed by addition of a cation exchange membrane (CEM) overlayer demonstrated high selectivity toward redox ion extraction and exclusion. For junctions formed using a Fumion®AEM phase and a Nafion®overlayer, [IrCl6]2−ions exchanged into Fumion®prior to Nafion®overcoating remained entrapped and the Fumion®excluded [Ru(NH3)6]3+ions for durability testing periods of more than 20 h under conditions of interest for eventual
in situ spectral measurements. Experiments with the Sustainion®anion exchange ionomer uncovered evidence for [IrCl6]2−ion coordination to pendant imidazolium groups on the polymer. A cyclic voltammetric method for estimation of the effective diffusion coefficient and equilibrium extraction constant for redox active probe ions within inert, uniform density electrode-supported thin films was applied to examine charge transport mechanisms.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D0TC03309J
