FULL PAPER
Porous Films
Photoelectric Synergetic Responsive Slippery Surfaces
Based on Tailored Anisotropic Films Generated by
Interfacial Directional Freezing
Zubin Wang, Yao Liu, Pu Guo, Liping Heng,* and Lei Jiang
Smart responsive slippery surfaces are highly desirable for their potential
applications in many fields. Although slippery surfaces that respond to a
single external stimulus are reported, challenges in fabricating synergetic
responsive anisotropic slippery surfaces remain due to limitations in the
preparation of the underlying anisotropic substrate. Here, photoelectric
synergetic responsive slippery surfaces are fabricated based on anisotropic
porous films that are tailored by using an interfacial directional freezing
technique using a poly(3-hexylthiophene-2,5-diyl)/[6,6]-phenyl-C61-butyric
acid methyl ester (P3HT/PCBM) binary system. The anisotropic surface
structure of P3HT/PCBM films is facilely tailored by simply tuning the
freezing speed, the P3HT/PCBM mass ratio, and the total concentration
of solution. A detailed formation mechanism is proposed and elucidated.
Moreover, anisotropic slippery surfaces demonstrate remarkable
photoelectric synergetic behavior, which is used for the photoelectric
synergetic control of droplet sliding and interfacial sentinel oxidative
degradation. The in-depth understanding of the formation mechanism of
the anisotropic porous film may enable the interfacial directional freezing
method to be extended to the design of other multifunctional anisotropic
surfaces. This work will provide a theoretical basis for the design of new
types of smart slippery surfaces, which are potentially useful in microfluidics,
lab-on-chips, photoelectric displays, interfacial microreactors, and other
related fields.
1. Introduction
Many aligned anisotropic surfaces with different functionali-
ties have evolved in natural creatures. For instance, anisotropic
surfaces allow water striders to walk on water,[1] facilitate the
shedding of water from rice leaves to root,[2] favor the direc-
tional shedding of water droplets from butterfly wings and
Dr. Z. B. Wang, Dr. Y. Liu, Dr. P. Guo, Prof. L. P. Heng, 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
Beijing Advanced Innovation Center for Biomedical Engineering
Beihang University
Beijing 100191, China
E-mail: henglp@iccas.ac.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.201801310.
DOI: 10.1002/adfm.201801310
Adv. Funct. Mater. 2018, 1801310 1801310  (1 of 10)
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maintain their dryness even in rainy envi-
ronments,[3] and enable Nepenthes pitcher
plants to facilely capture prey due to their
anisotropic slippery peristom surfaces.[4–6]
These natural anisotropic surfaces have
attracted considerable academic interest,
and several of their structures and func-
tions have been mimicked.[7–15] Inspired
by the slippery peristome of Nepenthes
pitcher plants, Wong and co-workers
introduced the first paradigm of liquid-
infused slippery surfaces.[16] The prom-
ising slippery surfaces have attracted
widespread attention due to several of
their state-of-art properties: the ability to
repel arbitrary low-surface-tension liq-
uids, low contact angle (CA) hysteresis,
the self-cleaning property, and defect-
free features.[16] They have also attracted
attention due to their wide application
in fields as diverse as anti-icing,[17] anti-
fouling,[18,19] drag reduction,[20] anticor-
rosion,[21] the smart control of liquid
movement by external stimuli, and other
related fields.[22–27] The underlying sub-
strates used in the above work are all
isotropic porous materials with micro/
nanoscale roughness,[28–32] which is a
necessary condition to achieve slippery
surfaces. Although anisotropic substrates with microscale
roughness have been widely reported, anisotropic porous
substrates with micro/nanoscale roughness, which is the key
property in creating smart anisotropic slippery surfaces, have
rarely been reported (especially for smart polymers) due to the
limitations in fabrication technology.
Directional freezing technique known as ice-templating is
a powerful approach for fabricating anisotropic porous bulk
materials, such as aerogels with anisotropic vertically elon-
gated macrochannels,[33] monolithic silica microhoneycombs
with aligned channels,[34] nacre-mimetic graphene/poly(vinyl
alcohol) composite films, and Thalia dealbata stem-mimetic
graphene aerogel monoliths.[35,36] However, the reported
porous bulk materials fabricated using this directional
freezing technique exhibited anisotropic surfaces only after
they had been cut open, making them unsuitable for use in
interfacial investigations. To overcome this limitation, our
group has fabricated several different anisotropic porous films
with micro/nanoscale roughness using interfacial freezing
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technique,[37–40] which were used to prepare anisotropic slip-
pery surfaces via infusing lubricants into the films. Electri-
cally responsive slippery surfaces were prepared by using
conductive anisotropic porous films, and then the movement
of conductive liquid droplets could be reversibly controlled on
slippery surfaces under the application of voltage.[37] On this
basis, we studied the effect of the lubricant conductivity on
the electroresponsive behavior of the slippery surface, as well
as the influencing factors and mechanism of their anisotropic
self-cleaning.[38] Then, we further explored the effect of lubri-
cant viscosity and thickness on the electroresponsive behavior
and self-healing property of the slippery surface.[39] Further-
more, we fabricated temperature-responsive slippery surface
by using paraffin as lubricant and achieved the temperature
control of droplet transmission on the slippery surface and in
the tube.[40] Although some progress has been made in aniso-
tropic smart slippery surface, methods to controllably fabricate
anisotropic porous films by interfacial directional freezing and
the mechanism underlying this fabrication method are not
known. In addition, all reported smart responsive slippery
surfaces are all responsive to only one kind of external stim-
ulus, such as temperature,[23,40] magnetic field,[24–26] electric
field,[27,37–39] and mechanical force.[22] But in practical applica-
tions, such as chemical sensing and analysis, precisely cap-
turing and releasing droplets in intelligent microfluidics and
controllable drug delivery, the conditions are usually more
complicated, these single-responsive slippery surfaces cannot
satisfy the needs of double or synergetic stimulation in com-
plex environments. It is therefore desirable to design double
or synergetic responsive slippery surfaces that have more
advanced functions and integrated properties, including intel-
ligence, controllability, and suitability for complex external
environments. To the best of our knowledge, precisely fabri-
cating synergetic responsive anisotropic films for slippery sur-
faces and achieving synergetic control of liquid sliding are the
remaining challenges.
Herein, we demonstrate photoelectric synergetic responsive
slippery surfaces based on anisotropic films that are tailored by
interfacial directional freezing technique using a p–n heteroge-
neous poly(3-hexylthiophene-2,5-diyl)/[6,6]-phenyl-C61-butyric
acid methyl ester (P3HT/PCBM) binary system. By tuning the
fabrication parameters such as freezing speed, P3HT/PCBM
mass ratio and total concentration of solution, we can control-
lably assemble the long-chain (P3HT) and short-chain (PCBM)
components into anisotropic films. The mechanism of ori-
ented tuning the surface structure in binary systems has also
been deeply studied. Meanwhile, anisotropic slippery surfaces
based on tailored anisotropic porous films show remarkable
anisotropic wettability and photoelectric synergetic responsive
anisotropic droplet sliding behavior. When a light is alternately
turned on and off, photoelectric synergetic control of droplets
sliding on the anisotropic P3HT/PCBM slippery surfaces occurs
under an applied voltage. Moreover, based on the controllable
droplet movement, the slippery surfaces can also be used for
interfacial sentinel oxidative degradation of organic contami-
nants. The findings in this work should pave a promising way
to investigate the synergetic control of liquid sliding and pro-
mote related applications of controllable fluidic interfaces.
2. Results and Discussion
2.1. Fabrication of Aligned Anisotropic P3HT/PCBM
Porous Films
A binary system with the typical photoelectric molecules P3HT
(p-type) and PCBM (n-type) was selected to generate photoelec-
tric synergetic responsive films.[41] Here, an interfacial direc-
tional freezing technique was used to fabricate anisotropic
surfaces.[37,38] The preparation process is shown in Figure 1a and
was briefly divided into three steps. First, polymer solutions of
different concentrations and various P3HT/PCBM mass ratios

Figure 1.  a) Schematic of the process used for preparing P3HT/PCBM directional porous films: spin coating, interfacial directional freezing, and freeze-
drying. SEM images of the directional P3HT/PCBM porous films prepared from solution with a P3HT/PCBM mass ratio of 1:1 and a total concentra-
tion of 4 mg mL−1 at freezing speeds of b) 10, c) 5, d) 3, and e) 1.5 mm s−1. Freezing speed refers to the speed of immersing the liquid coatings into
liquid nitrogen. At a high freezing speed (10 mm s−1), the prepared film structures were less anisotropic. When the freezing speed was 3 mm s−1, the
films were composed of parallel ridges in the longitudinal direction and porous fibers in the transverse direction. At a freezing speed of 1.5 mm s−1,
only longitudinal ridges were found in the films.

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were spin coated on indium tin oxide (ITO) substrate. Next, the fibers grow and ridges become thin (Figure S1c, Supporting
ITO substrates coated with the liquid were vertically immersed Information). A pure P3HT film was prepared from a solution
in liquid nitrogen at various speeds. After the liquid coating was with a concentration of 4 mg mL−1 (Figure S1d, Supporting
frozen, the sample was placed in the liquid nitrogen to keep the Information), but forming a porous structure was difficult due
coating from melting. Finally, the sample was transferred to a to the high concentration of P3HT, which is consistent with
freeze-drying machine, and the solid solvents became gas at low results in our previous report.[37] A comparison of the struc-
temperature and under vacuum to yield the anisotropic porous tures in Figure S1a–d in the Supporting Information shows
films. The P3HT/PCBM mass ratio, the concentrations of solu- that the short-chain precursor (PCBM) tends to be assembled
tion, and the freezing speed during freezing stage control the in the ridges and that the fibers located between the ridges
fabrication process for the as-prepared surface structure[42] are mainly the long-chain precursor (P3HT). To determine the
and were thus systematically studied. The speed of vertical effect of the total concentration of P3HT/PCBM, we also used
immersion was defined as the freezing speed. Figure 1b–e solutions with concentrations of 2, 3, 6, and 8 mg mL−1 at a
shows top-view scanning electron microscopy (SEM) images of mass ratio of 1:1 to fabricate films (Figure S1e–h, Supporting
films prepared at different freezing speeds using solutions with Information). Only the solution with 4 mg mL−1 total precur-
a total concentration of 4 mg mL−1 and a P3HT/PCBM mass sors at a mass ratio of 1:1 provided aligned anisotropic porous
ratio of 1:1. When the freezing speed was 10 mm s−1, P3HT/ surfaces; concentrations that are too high or low either lead to
PCBM nanofibers with diameters of ≈50–200 nm were dis- discontinuous network structures with large areas of substrate
tributed randomly, giving a slight structural disparity in both exposure or produce surfaces with a host of sheet structures.
transverse and longitudinal directions and a less anisotropic
structure (Figure 1b). When the freezing speed was deceler-
ated to 5 mm s−1, the sample forms partially orderly structures 2.2. Formation Mechanism of the Anisotropic
in the longitudinal direction, and an anisotropic surface struc- P3HT/PCBM Films
ture appears (Figure 1c). However, the structure is not perfect,
having many unselective parts. When the freezing speed was Based on the above experimental results, a formation mecha-
reduced to 3 mm s−1, aligned elongated ridges appear in the nism is proposed and discussed in detail. Figure 2 shows sche-
longitudinal direction with diameters in the range of 1–3 µm; matic diagrams of the directional freezing process at various
in this case, fibers with diameters of ≈200–500 nm are retained freezing speeds. When the liquid coating is immersed into
in the spaces between the ridges, forming a ladder-like structure liquid nitrogen at high speed, the solvents immediately freeze;
(Figure 1d). Further reducing the freezing speed to 1.5 mm s−1, however, they freeze too fast for solvent crystals to grow direc-
as shown in Figure 1e, results in the disappearance of fibers in tionally, forming enormous amounts of small solvent crystals
the spaces between the ridges; meanwhile, the ridges in the lon- and resulting in P3HT and PCBM randomly locked between
gitudinal direction became thicker, with widths of 2–5 µm. The and in regions of frozen solvents (Figure 2a). In this case, the
surface structures of P3HT/PCBM films converted to micro- frozen liquid coating forms a disordered surface structure after
groove-like anisotropic structures. In addition, the ridges had solvent crystals sublimate during freeze-drying (Figure 1b).
an abundance of pores. These results indicate
that aligned anisotropic P3HT/PCBM porous
films with a network structure can be gener-
ated when the freezing speed is suitable.
To further explore the factors influencing
the fabrication of anisotropic surfaces, we
prepared various surfaces using solutions
with different mass ratios of P3HT/PCBM.
Surfaces were frozen at a rate of 3 mm s−1
using different solutions, which contain
pure PCBM, P3HT/PCBM at mass ratios
of 1:2 and 2:1, and pure P3HT with a total
concentration of 4 mg mL−1. As shown in
Figure S1a–d in the Supporting Informa-
tion, all the as-prepared P3HT/PCBM films Figure 2.  Schematic diagrams of binary system molecular orientation in directional porous
films prepared at a a) high freezing speed, b) medium freezing speed, and c) low freezing
demonstrate distinct structural anisotropy. speed. The solvents and solutes were immediately frozen when they were immersed into liquid
When there was no P3HT, the as-prepared nitrogen at high freezing speeds, so long-chain (P3HT) and short-chain (PCBM) precursors
surface was composed of short fibers in the were randomly distributed in the porous film and formed a disordered porous structure. When
ridges and fewer fibers between the ridges, the freezing speed is medium, most of the short-chain molecules and a small portion of the
possibly resulting from the short-chain pre- long-chain molecules are squeezed out by the crystal templates of solvent to form a directional
cursor (PCBM) being dominant. At a higher ridge. During the exclusion process, most of the long-chain molecules are locked at the stage
of forming solvent crystals and are then stretched transversely during the growth of solvent
proportion of P3HT (mass ratio of 1:2),
crystals to form a transverse fiber structure. When a low freezing speed is used, the solute
fiber-like structures grow between the ridges molecules are fully excluded by the crystal templates of solvents because the slow growth speed
(Figure S1b, Supporting Information). As the of the crystal template provides enough time for molecular chain movement and migration,
P3HT proportion increases, more transverse resulting in the formation of only parallel ridge-like structures.

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Directional freezing of the liquid coating at medium speed
leads to the growth of solvent crystals that exclude some P3HT
and PCBM molecules to assemble into the ridges between the
formed solvent crystals. At this freezing speed, some of the
long-chain molecules are locked in the stage of forming sol-
vent crystals and then stretched transversely during the growth
of solvent crystals,[43] making them difficult to be excluded
(Figure 2b). After the solvent crystals sublimate, an aligned ani-
sotropic surface with fibers is then located in the gaps between
the ridges (Figure 1d). Further reducing the freezing speed pro-
vides enough time for solvent crystals to grow,[44] which allows
all the molecular chains to move and migrate during the growth
of solvent crystals (Figure 2c). After these molecules are fully
squeezed out, they are condensed between the solvent crystals,
yielding thick ridges and almost no fibers between the ridges
after sublimation (Figure 1e). The anisotropy of the obtained
surface structure will thus increase as the directional freezing
speed slows.
However, aligned anisotropic surfaces with network struc-
tures are difficult to produce when the mass ratio of the
precursors is not 1:1 and the freezing speed is 3 mm s−1
(Figure S1a–d, Supporting Information), which may be mainly
due to the effect of the solution properties on crystal nucleation
and growth.[44,45] The viscosity of solutions containing a high
proportion of PCBM (pure PCBM) is low, and the short-chain
molecules are more easily excluded when the solvent crystals
grow,[44,45] producing no transverse fibers and thick ridges
(Figure S1a, Supporting Information). Increasing the propor-
tion of P3HT (mass ratio of 1:2) increases the viscosity of the
solution and makes the long-chain molecules more likely to be
locked in the solvent crystal when they grow,[45,46] resulting in
transverse fiber structures (Figure S1b, Supporting Informa-
tion). The higher viscosity induced by the large proportion of
P3HT (mass ratio of 2:1) also causes large solvent crystal nuclei
to form in the initial freezing stage.[36] The long-chain mol-
ecules are consequently more likely to be trapped by the sol-
vent crystals and thus more difficult to be excluded, resulting
in greater transverse fiber density and thin ridges (Figure S1c,
Supporting Information). Most solvent crystals have difficulty
growing when only P3HT is in the solution due to the obstruc-
tion caused by the long-chain molecules, leading to the for-
mation of many fibers and no ridges in the anisotropic films
after sublimation (Figure S1d, Supporting Information). The
abovementioned discussion suggests that freezing speed and
the properties of the solution are important in the interfacial
freezing technique, yielding a guide to subtly optimize surface
anisotropic structures.
2.3. Fabrication of Anisotropic Slippery Surfaces
Taking into consideration the porous structure of the under-
lying film for fabricating anisotropic slippery surfaces, we
selected films that had been directionally frozen at 3 mm s−1
to be samples in the following experiments because their
groove-like parallel ridges provide anisotropy and network
structures can retain the lubricant (silicone oil) via capil-
lary force (Figure 1d). Before the pristine P3HT/PCBM films
were infused with silicone oil, their surface wettability, and
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droplet sliding behavior were characterized by measuring the
CAs and sliding angles (SAs) of water and silicone oil drop-
lets in both directions. Here, we defined the direction par-
allel to the ridges as the parallel direction and the other as
the perpendicular direction. Silicone oil droplets immediately
spread into the porous films once they had been deposited on
the films, giving CAs of nearly 0° in both directions (Figure
S2a,b, Supporting Information). The films gave water CAs
of 132.1°  ± 1.8° in the parallel direction and 140.7°  ± 2.7° in
the perpendicular direction, giving a wetting anisotropy value
of 8.6° (Figure S2a,b, Supporting Information). The sliding
behavior of water droplets on the films is shown in Figure
S2c in the Supporting Information. The water droplets were
not shed off the film along the ridges, even the films titled
vertically, demonstrating that water droplets exhibit no sliding
behavior on the pristine P3HT/PCBM films.
Silicone oil was selected as the model lubricant in the fab-
rication of the anisotropic slippery surfaces. Silicone oil drop-
lets of 20 µL were spin coated on the films at a predetermined
rotational speed, creating uniform lubricant coating due to the
superoleophilicity of the films. We systematically explored the
relationship between the SAs in both directions and the spin-
coating speed to maximize the anisotropy of the slippery sur-
faces (Figure S3, Supporting Information). For a 2 µL water
droplet, the SAs in both directions are smaller than 5° when
the spin-coating speed is 1000 rpm and show small aniso-
tropic SA discrepancies that are due to the thick silicone oil
layer. The SAs in both parallel and perpendicular directions
increase with increasing spin-coating speed. The SAs in the
two directions result in a maximum discrepancy of 12.5°
when the spin-coating speed is 2500 rpm because the SAs are
29.2° ± 3.8° (parallel direction) and 41.7° ± 3.1° (perpendicular
direction) (Figure S5a,b, Supporting Information). The aniso-
tropic SA discrepancy of 12.5° is larger than that of natural rice
leaves.[2,7] When the spin-coating speed had been increased to
7000 rpm, most silicone oil was removed from the porous net-
work due to the high shear force.[47] Droplets therefore barely
slid off in either direction when the surface was tilted at 90°.
The thickness of the silicone oil layer became thinner with
increasing spin-coating speed, increasing the friction force (f)
(Figure S4, Supporting Information, f1 < f2 < f3) and therefore
the SAs. Accordingly, the anisotropic SAs were closely linked
to the silicone oil layer. The infusion of thicker silicone oil
layers in the porous network hid the underlying anisotropic
surface structures, leading to the disappearance of anisotropic
droplet sliding behavior (Figure S4a, Supporting Information).
In contrast, slippery surfaces infused with traces of silicone oil
pin the droplet in both directions due to the exposure of sur-
face structure (Figure S4c, Supporting Information). Only the
suitable silicone oil layer therefore leads to large SA anisotropy
as well as anisotropic droplet sliding behavior (Figure S4b,
Supporting Information). According to the above discussion,
a spin-coating speed of 2500 rpm was selected to spin coat
the silicone oil into the P3HT/PCBM directional porous films,
yielding anisotropic slippery surfaces. The surface wettability
of the anisotropic slippery surfaces was also characterized,
giving a CA in the parallel direction of 102.1° ± 1.6° and a CA
in the perpendicular direction of 104.5°  ± 2.4° (Figure S5c,d,
Supporting Information).
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2.4. Photoelectric Synergetic Responsive CAs and SAs
on the Anisotropic Slippery Surfaces
With respect to the significant goal of achieving the photo-
electric synergetic control of droplet movement, CA and SA
transitions on the anisotropic slippery surfaces were system-
atically studied under applied voltages with and without light
irradiation (Figure 3). An experimental apparatus with a pre-
installed conductive copper wire was used to measure the
variations in CAs and SAs under applied voltage in this study,
which was similar to the approach taken in our previous work
(Figure 3a).[37] When 2.0 V was applied, the CAs of water
decreased from 102.5°  ± 2.3° to 75.8°  ± 2.5° in the parallel
direction and from 105.6°  ± 2.7° to 78.1°  ± 3.1° in the per-
pendicular direction with increasing light intensity from 0 to
100 mW cm−2 (Figure 3b). Because the copper wire provided
an additional f and hindered the sliding of droplets on slippery
surfaces, the initial SAs in both the parallel and perpendicular
directions were larger than those obtained without copper
wire (Figure S3, Supporting Information). Under an applied
voltage of 2.0 V, the SAs of water droplets increased from
35.6° ± 2.4° in the parallel direction and 49.9° ± 3.1° in the per-
pendicular direction to 90° with an increase in light intensity
from 0 to 100 mW cm−2 (Figure 3c). When the light intensity
was 40 mW cm−2, the SAs in the parallel and perpendicular
directions were 51.3°  ± 2.5° and 63.5°  ± 2.4°, respectively,

Figure 3.  a) Schematic diagram of slippery surface fabrication and photoelectric response measurements of SAs. Variation in b) CAs and c) SAs in both
directions as a function of light intensity with an applied voltage of 2.0 V. The results show that the CAs decreased and SAs increased with increasing
light intensity. Variation in SAs d) in the parallel (//) direction with and without light and e) in the perpendicular (⊥) direction with and without light are
shown. The SAs in both directions increased with continuously increasing applied voltage in both light and dark. According to the variation in SAs, the
applied voltage can be divided into three regions. In region I, the small applied voltage causes the SAs to barely change. In region II, the SAs increased
with increasing applied voltage under light, while the SAs remained constant in dark. In region III, SAs increased as the applied voltage increased in
both dark and light. Region II is suitable for the photoelectric synergetic control of water droplet sliding. The light intensity was 40 mW cm−2.

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and the appropriate SAs suggested that the light intensity of at 2.0 V, the SAs of water droplets reversibly switched between
40 mW cm−2 was suitable for the following photoelectric syn- two states when the surfaces were subjected to a light source
ergetic experiments. cycling on/off. With an applied voltage of 2.0 V, water droplets
As shown in Figure 3d,e, the SAs of water droplets in both on the anisotropic slippery surfaces were in the low-SA state
directions were systemically investigated with continuously (35.6° ± 2.4° in the parallel direction and 49.9° ± 3.1° in the per-
increasing voltages whether or not light was present. In the case pendicular direction) without light illumination; however, water
of no light irradiation, the SAs of water droplets on the aniso- droplets assumed the high-SA state (51.3° ± 2.5° in the parallel
tropic slippery surfaces were nearly constant in either direction direction and 63.5° ± 2.4° in the perpendicular direction) when
in the primary stage (0–2.5 V). When the applied voltage was light sources were on. The anisotropic SAs of the P3HT/PCBM
continuously increased from 2.5 V, the SAs in both directions slippery surfaces demonstrated durable reversible switching
increased (Figure 3d,e under dark conditions). This voltage is after 10 on/off light cycles.
denoted threshold voltage here. SAs increased from 37.5° ± 2.6° Based on the above experimental results, photoelectric coop-
(parallel direction) and 51.8° ± 2.5° (perpendicular direction) to erative capture/release of droplets on P3HT/PCBM slippery
90° when the voltage was increased from 2.5 to 6.5 V. When surface is possible. As a proof-of-concept, a 2 µL droplet of
the voltage was greater than 6.5 V, the water droplet did not water was deposited on the slippery surface under an applied
slide off and was pinned on the slippery surface even when the voltage of 2.0 V, and its sliding behavior was recorded as illumi-
surface was tilted at 90°. The minimum voltage that pinned the nation was turned on and off. As demonstrated in Figure 4a, a
water droplet (6.5 V) was denoted pinning voltage. In contrast, water droplet was deposited on a tilted slippery surface with a
when 40 mW cm−2 light illuminated water droplets, a primary tilt angle (TA) of 40°. The droplet easily slid off the surface in
stage was found in the range from 0 to 1.0 V in which the SAs the parallel direction once it fully touched the surface because
in both parallel and perpendicular directions almost did not the TA was larger than the SA of 35.6° ± 2.4°. When the light
change (Figure 3d,e under light conditions). The water SAs source was turned on, the water droplet slowed and eventually
changed from 35.6°  ± 2.4° to 90° in the parallel direction and stopped in a short time because the droplet assumed a high-SA
from 49.9° ± 2.3° to 90° in the perpendicular
direction with an increase in voltage from
1.0 to 4.5 V. Water droplets were similarly
fully pinned to the slippery surface under
applied voltages larger than 4.5 V and light
illumination at an intensity of 40 mW cm−2.
The SA variations shown in Figure 3d,e
indicate that the threshold and pining volt-
ages are smaller under light illumination
than in the dark. According to the variation
in SAs, the applied voltages can be divided
into three regions. In region I, whether there
was light or not, the SAs of water droplets
barely changed because the applied voltage
was smaller than the threshold voltage. In
region II, the SAs of water droplets increased
with increasing applied voltage under light
illumination, while the SAs remained con-
stant under dark conditions because the light
illumination reduced the threshold voltage.
In region III, SAs increased with or without
illumination with increasing applied voltage
because the applied voltage exceeded the
threshold voltage. Thus, the conditions of
region II are suitable for photoelectric syner- Figure 4.  a) Demonstration of photoelectric cooperative control of droplet motion in the par-
getic control of water droplet sliding. allel direction of the film given a TA of 40° and an applied voltage of 2.0 V; the light intensity is
−2
40 mW cm . b) Demonstration of photoelectric synergetic control of sentinel degradation of
organic contaminants. Before the liquid was dropped, a trace of sodium thiosulfate particles
was deposited on the slippery surface (red circle). A droplet (2 µL) of Fe2+-activated methylene
2.5. Photoelectric Synergetic Control blue (0.03 mg mL−1, dark blue) solution was deposited on the slippery surface, and the droplet
of Droplet Sliding and Its Application then slid toward the sodium thiosulfate particles. When the droplet slid close to sodium thio-
sulfate particles, a light of 40 mW cm−2 intensity was turned on, and the droplet was captured
Given the range of SA transitions in and began to react with sodium thiosulfate. After the oxidation reaction proceeded for ≈33 s,
the light was turned off, and the droplet slid again. After the reaction, the droplet was colorless.
response to voltage and light, 2.0 V and a
Due to the relatively high conductivity of the solution, a low applied voltage of 1.0 V was suit-
light intensity of 40 mW cm−2 were used for able. The results indicated that the photoelectric synergetic control of water droplet movement
the photoelectric synergetic study. Figure S6 had been achieved and that the slippery surface can be used for interfacial sentinel oxidative
in the Supporting Information shows that degradation of organic contaminants.

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state with an SA of 51.3°  ± 2.5°, and the SA was larger than
the TA. When the light was on, the droplet was pinned to the
slippery surface. When the light illumination was removed,
the droplet was released and began to slide again on the surface
because the SA converted to 35.6°  ± 2.4°. Based on the above
experimental results, photoelectric synergetic control of water
droplets sliding on a slippery surface under a given voltage was
achieved by alternating the light source on and off.
The photoelectric synergetic control of water droplet move-
ment renders the use of these slippery surfaces for interfacial
sentinel oxidative degradation of organic contaminants fea-
sible. Figure 4b shows a prototype demonstration of interfa-
cial sentinel oxidative degradation of an organic contaminant.
The detailed experiment was demonstrated in Section S1 in the
Supporting Information. To conduct the experiment, we prede-
posited a trace of oxidant (sodium persulfate) on the slippery
surface (Figure 4b). Under an applied voltage of 1.0 V (because
conductivity of the solution is higher than that of water, a low
applied voltage (1.0 V) is suitable for the photoelectric syner-
getic control of liquid movement (Figure S7, Supporting Infor-
mation)), a droplet of Fe2+-activated methylene blue solution
(0.03 mg mL−1, deep blue) was deposited on the tilted slippery
surface. Once it touched the surface, the methylene blue solu-
tion slid toward sodium persulfate particles. When the droplet
slid near to sodium persulfate particles, the light source was
turned on, and the droplet was captured to react with the
sodium persulfate. The light was turned off at ≈33 s, resulting
in the droplet sliding again, and the droplet had become color-
less during the reaction. Finally, the drop slid off surface due to
the surface’s excellent self-cleaning ability. The results strongly
demonstrate that the promising slippery surface can be used
for photoelectric synergetic control of the interfacial sentinel
degradation of organic contaminants and is suitable for other
chemical reactions and related applications.
2.6. Photoelectric Synergetic Responsive Mechanism
of the P3HT/PCBM Slippery Surfaces
To determine the photoelectric cooperative response mecha-
nism and the manner in which the external light reduced the
threshold voltage, we characterized the photoelectric properties
of the pristine P3HT/PCBM film and fully analyzed the fric-
tion forces and charge interactions between the water droplet
and the slippery surface. As shown in Figure 5, the pristine
P3HT/PCBM film, as a composite semiconductor film widely
used in photovoltaic devices,[41] shows excellent photocon-
ductivity in the visible region. The UV–vis diffuse reflectance
spectra in Figure 5a show that the P3HT/PCBM composite film
has less light reflection from 400 to 800 nm than the PCBM
film, indicating that P3HT strongly absorbs light in the UV–vis
region. The photocurrent action spectrum in Figure 5b shows
that the P3HT/PCBM film has a strong photoelectric response
in the region from 400 to 700 nm, showing that the films can
produce a photovoltage in response to light. Nyquist diagrams
of the impedance spectra obtained in dark and light (Figure 5c)
show that the P3HT/PCBM film had lower resistance in light
than in dark, which is due to the photocurrent generated by

Figure 5. The photoelectric properties of the as-prepared P3HT/PCBM directional porous films. a) UV–vis diffuse reflectance spectra of PCBM
and P3HT/PCBM directional porous films. b) IPCE spectrum of P3HT/PCBM directional porous film. c) The Nyquist diagrams of the impedance
spectra of P3HT/PCBM directional porous film in the dark and under light. d) Schematic energy level diagram and electron transfer process of the
P3HT/PCBM film.

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illumination. The energy level diagram and the electron transfer
process of the P3HT/PCBM film are presented in Figure 5d.
The schematic energy level diagram of the P3HT/PCBM film
indicates that the energy bands of P3HT and PCBM match.
Under light, P3HT molecules absorb photons and are excited
to create electron–hole pairs. The electrons transfer from the
lowest unoccupied molecular orbital (LUMO) of P3HT to the
LUMO of PCBM, and the holes jump from the highest occu-
pied molecular orbital of P3HT to the ITO conducting layer.
The additional photoelectrons have an important effect on the
interfacial charge interactions between the P3HT/PCBM film
and the water droplet.
Furthermore, the charge distribution of the system and the
forces loaded on the water droplet were analyzed in Figure 6 in
dark and light. As shown in Figure 6a, once the external voltage
was exerted in dark, the charges separated by the silicone oil
would distribute at the interface of the water droplet and the
P3HT/PCBM film, forming an electrical double layer.[48,49] Elec-
trons were photogenerated by light in the P3HT/PCBM films,
resulting in increased charge density in these films and there-
fore in the water droplet (Figure 6b). When the light was turned
off, the photogenerated electrons disappeared, and the charge
distribution returned to what it was in dark. The charge den-
sity significantly influences the electrostatic force (Fe) between
water droplets and P3HT/PCBM films. The friction force loaded
on the water droplet can be determined by the following equa-
tion: f  =  µN, where µ represents the friction coefficient and N
indicates the positive pressure. N is composed of components
of gravity (F2) and the electrostatic force (Fe) of the charges,
i.e., N  =  F2  +   Fe. The relatively low electrostatic force (Fed) in
dark produces a small positive force (Nd), which leads to a low
fd and SA (Figure 6c). When the surface is lit, the additional
photoelectrons in the P3HT/PCBM film enhance the electro-
static force (Fel) and therefore the positive pressure (Figure 6d).
The enhanced positive pressure produces a large friction force
(fl) and SA, which captures the water droplet and pins it to the
slippery surface. When the light was turned off, the additional
photoelectrons disappear, decreasing the positive pressure and
the friction force and releasing the water droplet.
3. Conclusion
In conclusion, we have successfully fabricated a photoelectric
synergetic responsive P3HT/PCBM slippery surface based on
tailored anisotropic films that are generated by an interfacial
directional freezing technique using a binary system. By care-
fully controlling the freezing speed, P3HT/PCBM mass ratio
and total solution concentration, the long-chain P3HT molecules
and short-chain PCBM molecules can be controllably assembled
into anisotropic films. Moreover, the formation mechanism
responsible for tuning the surface structure was also deeply
studied. More importantly, the slippery surfaces deriving from
the p–n heterogeneous conductive polymers showed distinct
anisotropic surface wettability and photoelectric synergetic
responsive droplet sliding behaviors. Based on the controllable
droplet sliding, the slippery surfaces can also be used for interfa-
cial sentinel oxidative degradation of organic contaminants sen-
tinel oxidation degradation by external applied
voltage and light. This work may provide a
new strategy for facilely obtaining anisotropic
porous surfaces, and the use of the photoelec-
tric synergetic responsive slippery surface can
be expanded to applications in controllable
liquid transport, water collection, microfluidic
channels, and other related fields.

4. Experimental Section
Materials and Sample Preparation: Commercially
available P3HT (99%, Sigma-Aldrich, China), [6,6]-
PCBM (99%, Sigma-Aldrich, China), chloroform
(99%, J&K Chemicals, China), 1,2-dichlorobenzene
(99%, J&K Chemicals, China), methylene blue
trihydrate (Sinopharm Chemical Reagent Co. Ltd,
China), iron powder, and sodium persulfate (98%,
Sinopharm Chemical Reagent Co. Ltd, China) were
Figure 6.  The charge distribution on the water droplet and P3HT/PCBM films a) without and used directly without further treatment. Silicone
b) with light under an applied voltage. a) When the external voltage is applied in dark, the oil with a viscosity of 20 cSt was purchased from
charges separated by the silicone oil distributed at the interface between the water droplet Zhongkeshangde, China. Water with a resistivity of
and the P3HT/PCBM film, forming an electrical double layer. b) In light, the photogenerated 18 MΩ cm was obtained from a Milli-Q purification
electrons were in the P3HT/PCBM films, resulting in increased charge density in the P3HT/ system (Millipore Corp., Bedford, MA, USA).
PCBM film and therefore in the water droplet. When the light was turned off, the photogen- Solutions with 2, 3, 4, 6, and 8 mg mL−1 total
erated electrons disappeared, and the charge distribution returned to what it was in dark. The precursors with a P3HT/PCBM mass ratio of
change in charge density induced by illumination significantly influences the electrostatic force. 1:1 were prepared by dissolving an appropriate
The forces loaded on the water droplet c) without and d) with light under an applied voltage amount of P3HT and PCBM in solvent. Moreover,
are shown. In dark, the friction force (fd) is determined by the perpendicular component of solutions at a total concentration of 4 mg mL−1
gravity (F2) and the electrostatic force (Fed). When the sample is illuminated, the increased with pure PCBM, P3HT/PCBM at mass ratios of
charge density induced by photogenerated electrons increases the electrostatic force (Fel) and 1:2 and 2:1, and pure P3HT were also prepared.
therefore fl and the SA. The solvent was obtained by mixing chloroform

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and 1,2-dichlorobenzene at a volume ratio of 1:9. To obtain the aligned
anisotropic porous polymer films, the solutions were spin coated on ITO
substrates at 800 rpm for 5 s with a spin coater (KW-4A, China), and
the ITO substrates were then immediately vertically immersed in liquid
nitrogen at different speeds. The immersion speed was defined as the
freezing speed. The samples were thus frozen in liquid nitrogen and
then freeze dried overnight to produce directional polymer films using
a freeze dryer (BEKO, Germany). Then, 20 µL of silicone oil was spin
coated on the P3HT/PCBM directional porous films at 1000, 1500, 2000,
2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, and 7000 rpm
for 20 s. All the P3HT/PCBM porous films used for preparing slippery
surfaces were obtained from the 4 mg mL−1 solutions with a P3HT/
PCBM ratio of 1:1, and the freezing speed was 3 mm s−1.
Sample Characterization: SEM images of the samples were captured
using an environmental scanning electron microscope (Quanta FEG250,
FEI) with a thin gold coating. The CAs and SAs were measured with a
Dataphysics OCA20 instrument (Germany). At least five different
positions of the same sample were measured and averaged to obtain
a reliable value. The photos in this work were taken by a digital camera
(Canon 6D, Japan). A solar simulator (CMH-250, Aodite Photoelectronic
Technology Ltd., Beijing) was used directly as the light source. The light
intensity was calibrated with a power and energy meter (Model FZ-A,
Beijing). The applied voltages in the SA measurements were obtained
directly from a DC power source (HB1700, China) without time steps to
achieve more exact data in the experiment. UV–vis spectra were collected
by combining the Optic Fiber Spectrum (NOVA, Idea Optics, Shanghai,
China) and optical microscopy. The incident photon-to-current conversion
efficiency (IPCE) for solar cells was determined using a commercial
setup (PV-25 DYE, JASCO; a 300 W Xenon lamp was employed as a light
source). Electrochemical impedance measurements were carried out with
an electrochemical workstation (CHI660E, China) at room temperature.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was supported by the National Natural Science Foundation
of China (51673010 and 51541301), the National Research Fund for
Fundamental Key Projects (2014CB931802), the Fundamental Research
Funds for the Central Universities (YWF-16-BJ-Y-72), the 111 Project
(B14009), and the National Key Research and Development Program of
China (2017YFA0206904).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
anisotropic porous films, droplet sliding, interfacial directional freezing,
photoelectric synergy, slippery surfaces
Received: February 19, 2018
Revised: April 7, 2018
Published online:
[1] X. F. Gao, L. Jiang, Nature 2004, 432, 36.
[2] L. Feng, S. H. Li, Y. S. Li, H. J. Li, L. J. Zhang, J. Zhai, Y. L. Song,
B. Q. Liu, L. Jiang, D. B. Zhu, Adv. Mater. 2002, 14, 1857.
Adv. Funct. Mater. 2018, 1801310 1801310  (9 of 10)
www.afm-journal.de
[3] Y. M. Zheng, X. F. Gao, L. Jiang, Soft Matter 2007, 3, 178.
[4] U. Bauer, W. Federle, Plant Signaling Behav. 2009, 4, 1019.
[5] H. W. Chen, P. F. Zhang, L. W. Zhang, H. L. Liu, Y. Jiang, D. Y. Zhang,
Z. W. Han, L. Jiang, Nature 2016, 532, 85.
[6] H. F. Bohn, W. Federle, Proc. Natl. Acad. Sci. USA 2004, 101, 14138.
[7] D. Wu, J.-N. Wang, S.-Z. Wu, Q.-D. Chen, S. Zhao, H. Zhang,
H.-B. Sun, L. Jiang, Adv. Funct. Mater. 2011, 21, 2927.
[8] S. G. Lee, H. S. Lim, D. Y. Lee, D. Kwak, K. Cho, Adv. Funct. Mater.
2013, 23, 547.
[9] X. Yao, Q. W. Chen, L. Xu, Q. K. Li, Y. L. Song, X. F. Gao, D. Quéré,
L. Jiang, Adv. Funct. Mater. 2010, 20, 656.
[10] J. Zhang, Z. Cheng, Y. Zheng, L. Jiang, Appl. Phys. Lett. 2009, 94,
144104.
[11] C. X. Li, N. Li, X. S. Zhang, Z. C. Dong, H. W. Chen, L. Jiang, Angew.
Chem., Int. Ed. 2016, 55, 14988.
[12] C. X. Li, L. Wu, C. L. Yu, Z. C. Dong, L. Jiang, Angew. Chem., Int. Ed.
2017, 56, 13623.
[13] P. F. Zhang, L. W. Zhang, H. W. Chen, Z. C. Dong, D. Y. Zhang, Adv.
Mater. 2017, 29, 170295.
[14] P. F. Zhang, H. W. Chen, L. Li, H. L. Liu, G. Liu, L. W. Zhang,
D. Y. Zhang, L. Jiang, ACS Appl. Mater. Interfaces 2017, 9, 5645.
[15] L. R. Shang, Y. R. Yu, W. Gao, Y. T. Wang, L. L. Qu, Z. Zhao, R. J. Chai,
Y. J. Zhao, Adv. Funct. Mater. 2018, 28, 1705802.
[16] T.-S. Wong, S. H. Kang, S. K. Y. Tang, E. J. Smythe, B. D. Hatton,
A. Grinthal, J. Aizenberg, Nature 2011, 447, 443.
[17] P. Kim, T. S. Wong, J. Alvarenga, M. J. Kreder, W. E. Adorno-Martinez,
J. Aizenberg, ACS Nano 2012, 6, 6569.
[18] U. Manna, N. Raman, M. A. Welsh, Y. M. Zayas-Gonzalez,
H. E. Blackwell, S. P. Palecek, D. M. Lynn, Adv. Funct. Mater. 2016,
26, 3599.
[19] S. Sunny, G. Cheng, D. Daniel, P. Lo, S. Ochoa, C. Howell, N. Vogel,
A. Majid, J. Aizenberg, Proc. Natl. Acad. Sci. USA 2016, 113, 11676.
[20] Y. Wang, H. F. Zhang, X. W. Liu, Z. P. Zhou, J. Mater. Chem. A 2016,
4, 2524.
[21] J. Lee, S. Shin, Y. H. Jiang, C. Jeong, H. A. Stone, C.-H. Choi, Adv.
Funct. Mater. 2017, 27, 1606040.
[22] X. Yao, Y. H. Hu, A. Grinthal, T.-S. Wong, L. Mahadevan,
J. Aizenberg, Nat. Mater. 2013, 12, 529.
[23] X. Yao, J. Ju, S. Yang, J. J. Wang, L. Jiang, Adv. Mater. 2014, 26, 1895.
[24] D. L. Tian, N. Zhang, X. Zheng, G. L. Hou, Y. Tian, Y. Du, L. Jiang,
S. X. Dou, ACS Nano 2016, 10, 6220.
[25] Y. Huang, B. B. Stogin, N. Sun, J. Wang, S. K. Yang, T.-S. Wong, Adv.
Mater. 2017, 29, 1604641.
[26] M. Y. Cao, X. Jin, Y. Peng, C. M. Yu, K. Li, K. S. Liu, L. Jiang, Adv.
Mater. 2017, 29, 1606869.
[27] J. Wang, L. Y. Sun, M. H. Zou, W. Gao, C. H. Liu, L. R. Shang,
Z. Z. Gu, Y. J. Zhao, Sci. Adv. 2017, 3, e1700004.
[28] P. Kim, M. J. Kreder, J. Alvarenga, J. Aizenberg, Nano Lett. 2013, 13,
1793.
[29] J. Kamei, H. Yabu, Adv. Funct. Mater. 2015, 25, 4195.
[30] A. B. Tesler, P. Kim, S. Kolle, C. Howell, O. Ahanotu, J. Aizenberg,
Nat. Commun. 2015, 6, 8649.
[31] U. Manna, D. M. Lynn, Adv. Mater. 2015, 27, 3007.
[32] K. Manabe, T. Matsubayashi, M. Tenjimbayashi, T. Moriya, Y. Tsuge,
K.-H. Kyung, S. Shiratori, ACS Nano 2016, 10, 9387.
[33] Y. Si, X. Q. Wang, C. C. Yan, L. Yang, J. Y. Yu, B. Ding, Adv. Mater.
2016, 28, 9512.
[34] H. F. Zhang, I. Hussain, M. Brust, M. F. Butler, S. P. Rannnard,
A. I. Cooper, Nat. Mater. 2005, 4, 787.
[35] N. F. Zhao, M. Yang, Q. Zhao, W. W. Gao, T. Xie, H. Bai, ACS Nano
2017, 11, 4777.
[36] M. Yang, N. F. Zhao, Y. Cui, W. W. Gao, Q. Zhao, C. Gao, H. Bai,
T. Xie, ACS Nano 2017, 11, 6817.
[37] T. Q. Guo, P. D. Che, L. P. Heng, L. Z. Fan, L. Jiang, Adv. Mater.
2016, 28, 6999.
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
[38] P. D. Che, L. P. Heng, L. Jiang, Adv. Funct. Mater. 2017, 27,
1606199.
[39] Z. B. Wang, L. P. Heng, L. Jiang, J. Mater. Chem. A 2018, 6, 3414.
[40] L. L. Wang, L. P. Heng, L. Jiang, ACS Appl. Mater. Interfaces 2018,
10, 7442.
[41] G. Li, R. Zhu, Y. Yang, Nat. Photonics 2012, 6, 153.
[42] S. Deville, Adv. Eng. Mater. 2008, 10, 155.
[43] K. L. Scotti, D. C. Dunand, Prog. Mater. Sci. 2018, 94, 243.
[44] S. Deville, J. Mater. Res. 2013, 28, 2202.
Adv. Funct. Mater. 2018, 1801310 1801310  (10 of 10)
www.afm-journal.de
[45] S. Deville, E. Saiz, R. K. Nalla, A. P. Tomsia, Science 2006, 311, 515.
[46] S. Deville, E. Maire, G. Bernard-Granger, A. Lasalle, A. Bogner,
C. Gauthier, J. Leloup, C. Guizard, Nat. Mater. 2009, 8, 966.
[47] N. Vogel, R. A. Belisle, B. Hatton, T.-S. Wong, J. Aizenberg, Nat.
Commun. 2013, 4, 2176.
[48] F. Bonaccorso, L. Colombo, G. H. Yu, M. Stoller, V. Tozzini,
A. C. Ferrari, R. S. Ruoff, V. Pellegrini, Science 2015, 347, 6217.
[49] F. Béguin, V. Presser, A. Balducci, E. Frackowiak, Adv. Mater. 2014,
26, 2219.
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim