Conspectus
Single crystals of organic semiconductors (OSCs)
are believed to
have both high mobility and intrinsic flexibility, making them promising
candidates for flexible electronic/optoelectronic applications and
being consistently pursued by researchers. The van der Waals force
in OSC enables low-temperature solution processing of single crystals,
but the relatively weak binding energy brings challenges in forming
large, uniform, and defect-free single crystals. To promote the study
on OSC single crystals, a generalized method that grows high-quality
crystals in an easy-to-handle, time/resource-saving, and repeatable
manner is apparently necessary. In 2012, Li et al. developed a droplet-pinned
crystallization (DPC) method that uses a rather simple strategy to
create a steadily receding contact line for the growth of OSC single
crystals. Instead of setting up expensive equipment, controlling strict
deposition parameters, or waiting for days or weeks for countable
crystal seeds, the DPC method offers a time- and cost-effective way
to obtain OSC single crystals for further study of the tendency of
crystallization, single-crystal mobility, and molecular packing information.
The DPC method is primarily a powerful tool for studying the charge-transport
mechanisms in OSC single crystals. In pioneering work, high-mobility
single crystals of both p-type 6,13-bis(triisopropylsilylethynyl)
pentacene (TIPS-PEN) and n-type C60 materials were obtained.
Driven by the demands from practical applications, we then focused
on the general lagging of electron mobility in OSC materials. The
ambipolar property of TIPS-PEN was studied, and a strong correlation
between electron mobility and polar species (polar solvent residuals
and surface hydroxyl groups) was observed. The latter further guided
the harvest of electron mobility in a series of OSC materials. Undoubtfully,
the facile DPC method accelerated these studies by providing a time-efficient,
reliable, and repeatable testing platform. Additionally, flexibility
on OSC materials and solvents, where not only one-component but also
binary systems were allowed, is another critical integrity of the
DPC method. The m-xylene/carbon tetrachloride binary
solvent was proven to be efficient for growing ribbon-like C60 single crystals rather than needle-like crystals from typical one-component
solvents. Afterward, a variety of OSC materials (including p-type,
n-type, and ambipolar ones) and a series of solvents (including aromatic,
aliphatic, and polar ones) were studied. The crystallization of OSC
single crystals was primarily found at either the top liquid–air
interface or the bottom solid–liquid interface. The interactions
between OSC molecules and substrate surfaces were deduced as the qualitative
determining factor. By utilizing the top interface crystallization,
the two-step sequential deposition of single-crystalline OSC heterojunctions
was enabled. Moreover, by selecting appropriate pairs of OSC materials that crystallize at separate interfaces,
the facile one-step formation of...