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1701861 (1 of 7)
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NANO MICRO
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2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Regular Aligned 1D Single-Crystalline Supramolecular
Arrays for Photodetectors
Yun Liu, Jiangang Feng, Bo Zhang, Yuchen Wu,* Yong Chen,* and Lei Jiang
Dr. Y. Liu
Beijing National Laboratory for Molecular Sciences (BNLMS)
Key Laboratory of Green Printing, Institute of Chemistry
Chinese Academy of Sciences
Beijing 100190, P. R. China
Dr. Y. Liu, Dr. J. G. Feng, Prof. L. Jiang
University of Chinese Academy of Science
Beijing 100049, P. R. China
Dr. J. G. Feng, Dr. Y. C. Wu, Prof. Y. Chen, Prof. L. Jiang
Key Laboratory of Bio-Inspired Materials and Interfacial Science
Technical Institute of Physics and Chemistry
Chinese Academy of Sciences
Beijing 100190, P. R. China
E-mail: wuyuchen@iccas.ac.cn; chenyong@mail.ipc.ac.cn
Dr. B. Zhang, Prof. L. Jiang
Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology
of Ministry of Education
Beijing Key Laboratory of Bio-Inspired Energy Materials and Devices
School of Chemistry
Beihang University
Beijing 100191, P. R. China
DOI: 10.1002/smll.201701861
Semiconducting supramolecular mate-
rials exhibit efficient exciton generation,
remarkable light sensitivity, and light
harvesting,
[1–4]
thus are ideal compo-
nents in applications such as phototran-
sistors,
[5]
field-effect transistors,
[6]
solar
cells,
[7,8]
and photovoltaic devices.
[9,10]
Distinguished from polycrystals, single
crystals possess long-range order, few
structural defects, and eliminated grain
boundary, which provide considerable
potential for achieving excellent device
performance.
[11–17]
Solution-processed
semiconducting materials have promising
advantages in terms of low-cost, large area,
and flexibility.
[15,18–22]
Therefore, various
patterning methods have been developed
such as drop casting, hollow pen writing,
and inject printing.
[23–28]
The micro/nano-
structure arrays could be obtained through
these solution method; however, it is hard
to control the molecular orientation in
micro/nanostructures due to the poorly
regulated fluid flow and fast solvent evapo-
ration process.
For conventional solution patterning
techniques, miniaturized liquid droplets or
thin films are located with predetermined patterns followed by
evaporation of solvents, dewetting, nucleation, and growth. The
dewetting process is dominated by isotropic and random capillary
flow, thus inducing random nucleation and growth of crystals at
gas–liquid–solid three-phase contact line (TCL). To obtain regular
patterned single-crystals with fine morphology and molecular
packing, unidirectional driving force is required to conquer the
coffee ring effect and regulate the dewetting dynamics, fluid flow,
mass transport, and crystallization process. Bao and co-workers
demonstrated a fluid-enhanced crystal engineering strategy by
harnessing the unidirectional shearing force to regulate the fluid
flow in solution process, yielding large-scale single-crystalline
thin films.
[29]
This method have succeed in guiding the unidi-
rectional dewetting process at the macroscale and achieving an
unprecedented mobility of the thin film devices.
In this work, we demonstrate an efficient and facile solution-
processing method for patterning organic single-crystalline
microstructures. An asymmetric-wettability micropillar tem-
plate with lyophobic tops and lyophilic sidewalls was intro-
duced to controlling the dewetting dynamics of molecule
solutions. Owing to the lyophobic tops, the liquid film is con-
fined in the gaps between each two micropillars, generating
Solution-processed semiconductor single-crystal patterns possess unique
advantages of large scale and low cost, leading to potential applications
toward high-performance optoelectronic devices. To integrate organic semi-
conductor micro/nanostructures into devices, various patterning techniques
have been developed. However, previous patterning techniques suffer from
trade-offs between precision, scalability, crystallinity, and orientation. Herein,
a patterning method is reported based on an asymmetric-wettability micro-
pillar-structured template. Large-scale 1D single-crystalline supramolecular
arrays with strict alignment, pure crystallographic orientation, and precise
position can be obtained. The wettability difference between tops and
sidewalls of micropillars gives rise to the confinement of organic solutions
in discrete capillary tubes followed by dewetting and formation of capillary
trailing. The capillary trailing enables unidirectional dewetting, regulated
mass transport, and confined crystal growth. Owing to the high crystal-
linity and pure crystallographic orientation with Pt atomic chains parallel to
the substrate, the photodetectors based on the 1D arrays exhibit improved
responsivity. The work not only provides fundamental understanding on the
patterning and crystallization of supramolecular structures but also develops
a large-scale assembly technique for patterning single-crystalline micro/
nanostructures.
Photodetectors
Small 2017, 1701861