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.
Organic semiconductors (OSCs) have shown great promise in a variety of applications. Although solution processing of OSCs has resulted in high‐quality films, exquisite control of structural development to minimize defect formation during large‐scale fabrication remains formidable. Compounding this challenge is the use of halogenated organic solvents, which poses significant health and environmental hazards. However, the solvent‐free techniques introduced thus far impose additional limitations on solidification kinetics; the resulting OSC thin films are often more defective than those processed from solution. Here, a solvent‐free technique is reported to prepare OSC membranes with centimetric crystalline domains. Leveraging the tendency for liquid crystalline materials to preferentially orient, OSCs are “prealigned” by depositing them from the melt over a metal frame to form a freely suspended membrane. Crystallization from this prealigned phase affords membranes with unprecedented structural order across macroscopic distances. Field‐effect transistors comprising membranes of dioctyl[1]‐benzothieno[3,2‐b][1]benzothiophene (C8BTBT) and didodecyl[1]‐benzothieno[3,2‐b][1]benzothiophene (C12BTBT) having centimeter‐sized domains as active layers exhibit a hole mobility of ≈8.6 cm2V−1s−1, superseding the mobility of any transistors whose active layers are deposited from melt. This technique is scalable to yield membranes with large crystalline domains over wafer dimensions, making it amenable for broad applications in large‐area organic electronics.
more » « less- Award ID(s):
- 1824674
- NSF-PAR ID:
- 10453888
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Electronic Materials
- Volume:
- 7
- Issue:
- 3
- ISSN:
- 2199-160X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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