Review

pubs.acs.org/CR

Breath Figure: A Nature-Inspired Preparation Method for Ordered

Porous Films
Aijuan Zhang, Hua Bai, and Lei Li*
College of Materials, Xiamen University, Xiamen, 361005, Peoples Republic of China
5.5. Interfacial Tension between Water Droplets
and the Polymer Solution AE
5.6. Deformation of BFA Films AF
5.7. Strategies for Perforated BFAs AG
5.8. Methods for Hierarchical BFA Films AH
5.9. Large-Scale Preparation of BFA Films AI
5.10. Other Methods AJ
6. Chemical Modication and Functionalization of
BFA Films AK
6.1. Functionalization of BFA Films AK
6.1.1. Hybridization with Inorganic Nanoma-
terials AK
6.1.2. Surface Chemical Modication AL
6.2. Cross-Linking of BFA Films AM
CONTENTS 6.2.1. Thermal Cross-Linking AM
6.2.2. Chemical Cross-Linking AM
1. Introduction A
6.2.3. Photochemical Cross-Linking AN
2. Preparation Methods for BFA Films C
7. Applications of BFA Films AP
2.1. Conventional BF Methods: Dynamic and
7.1. Templates AP
Static Processes C
7.2. Surface Enhanced Raman Scattering Sub-
2.2. Spin-Coating and Dip-Coating D
strates AR
2.3. Generalized BF Methods D
7.3. Separation AR
3. Formation Mechanism for BFA Films D
7.4. Optical and Optoelectronic Devices AS
3.1. Cooling of Solution and Nucleation of
7.5. Chemical Power Source AU
Moisture E
7.6. Micropatterning of Biological Molecules AV
3.2. Growth and Self-Assembly of Water Drop-
7.7. Cell Culture and Inhibition AW
lets F
7.8. Sensors AY
3.2.1. Shape of Water Droplets F
7.9. Miscellaneous Applications AY
3.2.2. Stability of Water Droplets G
8. Conclusion BA
3.2.3. Growth of Water Droplets I
Author Information BA
3.2.4. Assembly of Water Droplets K
Corresponding Author BA
3.3. Evaporation of Solvent and Water Droplets M
Author Contributions BA
4. Materials for BFA Films M
Notes BA
4.1. Linear Block Copolymers M
Biographies BB
4.2. Star and Branch Polymers R
Acknowledgments BB
4.3. Linear Homopolymers S
References BB
4.4. Biodegradable Polymers V
4.5. Microgels W
4.6. Nonpolymeric Materials X
4.6.1. Nanoparticles X 1. INTRODUCTION
4.6.2. Carbon Nanotubes and Graphene Y Nature provides inexhaustible inspiration to mankind. It
4.6.3. Small Organic Molecules Z continues to encourage us to develop new methods and
5. Morphological Control of BFA Films Z approaches to the construction of articial advanced materials.
5.1. Solvents Z For example, the self-cleaning of the lotus leaf originates from
5.2. Substrates AA the fractal structure features on the leaves combined with their
5.2.1. Materials of the Substrates AA waxy surface.1,2 Key advances in the understanding and
5.2.2. Shape of the Substrates AB fabrication of surfaces with controlled wettability are poised
5.3. Solution Concentrations AC to make the dream of a contamination-free (or no-clean)
5.4. Vapor Conditions AC
5.4.1. Water Vapor AC
Received: February 3, 2015
5.4.2. Nonaqueous Vapors AD

XXXX American Chemical Society A DOI: 10.1021/acs.chemrev.5b00069

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surface come true (Figure 1ac).35 In another example, the

mimicking of nacre enables the fabrication of bulk ceramics

Figure 2. (a) Dew on leaves. (b) Pouring collodion on the clean glass
substrate before making a wet-collodion negative.16 Reprinted with
permission ref 16. Copyright Freestyle Photographic Supplies.

contamination on glass substrates. In Figure 2b, a historical

picture demonstrates how to pour collodion onto a clean sheet
of glass to make negatives.16
For a long time, BF was considered an ordinary natural
phenomenon without practical applications in materials science.
Then, in 1994, Francois et al. reported the preparation of
polymeric porous lm with honeycomb structures by exposing
a drop of polystyrene-b-polyparaphenylene (PS-b-PPP, 1)
(Scheme 1) solution in carbon disulde (CS2) to a ow of
Figure 1. Examples of natural materials and nature-inspired materials
with high performance. (a, d, g) Photographs of natural materials:
lotus leaf (a), shell (d), and male Morpho didius buttery (g). (b, e, h) Scheme 1. Chemical Structure of PS-b-PPP (1)
Multiscale structures of the corresponding natural materials.1,6,9 (b)
Reprinted with permission from ref 1. Copyright 2009 The Royal
Society. (e) Reprinted with permission from ref 6. Copyright 2008
Elsevier. (h) Reprinted with permission from ref 9. Copyright 2002
The Royal Society. (c, f, i) Nature-inspired materials with super-
hydrophobicity and self-cleaning capacity (c),4 high mechanical
strength (f),7 and structure-based colors (i).10 (c) Reprinted with
permission from ref 4. Copyright 2002 Wiley-VCH. (f) Reprinted with
permission from ref 7. Copyright 2008 American Association for the
Advancement of Science. (i) Reprinted with permission from ref 10.
Copyright Donna Sgro.

without a ductile phase but with a unique combination of

strength (470 MPa), toughness (22 MPa m1/2), and stiness
(290 GPa).6,7 These ceramics retain their mechanical properties
at high temperature (600 C) (Figure 1df). MORPHOTEX is
an unstained, structurally colored ber.8 This technology is
based on the mimicking of the microscopic structure of the
morpho butterys wings.9 No dye or pigment is used. Instead,
color is created by varying the thickness and structure of the
bers (Figure 1gi).
The use of the breath gure (BF) method in materials
science, which is the topic of this review, is another example
where we learn from nature. BF refers to the fog that forms
when water vapor contacts a cold surface. BF is a commonly
observed phenomenon in daily life. One example is the fog that
appears on a window when we breathe on it. This is also the
origin of the name breath gure. Another example in nature is
the formation of dew, as shown in Figure 2a.11 The formation
of BF was rst investigated by John Aitken12,13 in 1895 and
later, in 1911, by Lord Rayleigh,14 who revealed the
morphology of water droplets on cold surfaces. Depending
on the wetting properties of the surface, the condensed uid
can form either a uniform lm, which appears dark (black BF),
or an assembly of droplets that scatter light and appear white
(gray BF).15 On clean hydrophilic glass, a uniform black BF is
expected. For the wet-plate photographic technique, a
scrupulously clean piece of clear glass is required. Therefore,
the BF method has been used since the 1850s by
photographers as a simple and eective way to detect oil
B DOI: 10.1021/acs.chemrev.5b00069
Figure 3. SEM image of PS-b-PPP BFA lm.17 Reprinted with
permission from ref 17. Copyright 1994 Nature Publishing Group.
moist air.17 As shown in Figure 3, the micrometer-sized pores
exhibited a highly regular hexagonal arrangement after removal
of the upper layer of these lms. The relationship between the
works of Lord Rayleigh and Francois was immediately
recognized: the hexagonally packed pores were the result of
BFs on the surface of the solution. Therefore, the ordered pore
arrays on the polymer lm prepared with this method were
named breath gure arrays (BFAs), and the lms were called
BFA lms. In the past two decades, this simple process has
been widely utilized as a versatile soft-template method for the
fabrication of honeycomb-patterned lms with controlled pore
size and dierent potential functions and applications, starting
from a variety of organic and inorganic materials. Compared
with the existing lithography techniques, including e-beam
lithography and scanning probe lithography, BF technique has
the following advantages: (1) very low costno complicated
instrument is needed, and the operation cost is also very low;
(2) time savingthousands of pores can be fabricated rapidly
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with one step in less than 5 min, in sharp contrast to e-beam
lithography and photolithography in which multistep processes
and much more time are involved; (3) easy implementation
no complex setup or environment control, such as vacuuming,
scanning electron microscopy (SEM), or clean room, is
necessary. Accordingly, the BF process has become a versatile
and handy strategy for the preparation of micropatterns and
porous materials in laboratories. Additionally, the BF process
has aroused the interest of industry: a patent by Fuji Film Co.
demonstrated their interest in equipment that could produce
BFA lms continuously on a commercial scale.18 The progress
of the BF technique in materials science up to early 2013 has
been summarized in several remarkable reviews.1928 However,
in the past two years, a great number of reports (over 100
papers) have been published, and these provide many new
insights into the mechanism of the BF process and show novel
and exciting applications of BFA lms. These publications have
demonstrated the rapid development of the BF technique and
have, to some extent, changed our understanding of this
technique. Therefore, it is necessary to give an overall review of
the BF technique based on the new ndings from recent
reports.
In this review, we will present a comprehensive summa-
rization on the state of the art in the preparation and
applications of porous materials (mainly lms) based on the BF
process. A historical account of important early studies is
included in this section, and the methods for preparing BFAs
are summarized in section 2. Although the preparation of BFAs
is quite simple, the mechanism of BFA formation is rather
abstruse due to the complex mass and heat transfer. In section
3, a comprehensive description of the formation mechanism is
presented. In the past 20 years, a number of polymeric and
nonpolymeric materials have been developed for the
construction of BFAs. This not only expands the applications
of BFAs but also facilitates understanding of the formation
mechanism. In section 4, the materials used in the literature to
fabricate BFAs are summarized. The morphological control of
BFAs, including the inuence of solvents, substrates, humidity,
gas ow, atmosphere, and solution concentration, and the
formation of BFAs with perforation and hierarchy, along with
other control methods, are discussed in section 5. The
functionalization and chemical modication of BFAs that are
described in section 6 are critical for the exploration of further
practical applications. The applications of BFAs in templating,
surface enhanced Raman scattering (SERS), separation, optical
and optoelectronic devices, electrode materials, and biology are
covered in section 7. Finally, a summary and an outlook on this
exciting eld are presented at the end of this review in section
8.
2. PREPARATION METHODS FOR BFA FILMS
BFA refers to the pore array generated by a water droplet array
condensed on a cold substrate. Therefore, the BF technique can
be dened as the process of preparing an ordered porous lm
with condensed water droplets as the template. According to
the above denition, the condensation of water vapor is the key
step in the BF process. There are other similar methods for
preparing porous lms in which the water droplet template is
generated by adding a certain amount of water. These are not
BF methods in the strictest sense, so they are set aside for a
brief discussion as complements at the end of the section.
C DOI: 10.1021/acs.chemrev.5b00069
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2.1. Conventional BF Methods: Dynamic and Static
Processes
In a conventional BF process, a drop of polymer (or other
substance) solution is cast onto a solid substrate and allowed to
evaporate in a humid environment.17 After the solvent and the
condensed water droplets evaporate completely, a porous lm
forms on the substrate. The process can be divided into
dynamic and static BF processes according to how the humid
environment is established.
In a dynamic BF process, the moisture is supplied by a gas
ow blown over the substrate (Figure 4a). This process was
Figure 4. Conventional BF methods. (a) Dynamic and (b) static BF
processes.
rst used by Francois et al. in their rst publication on BFAs.17
They produced BFAs by evaporating a solution of polymer 1 in
CS2 under a ow of moist gas. In a dynamic process, the
velocity of the ow and the humidity can be tightly controlled,
thus allowing the ne-tuning of the evaporation rate of the
solvent and the morphology of the BFAs17,2932 (see section
3.2.3 for details).
In a static BF process, the evaporation of solvent is
completed spontaneously without the aid of gas ow. Several
researchers, including Shimomura3335 and Stenzel,19,36 pre-
pared BFAs in their early studies with dierent polymers in a
static humid environment. Recently, our group optimized this
method and used it to fabricate various BFA lms.3740 In a
typical static BF process, the humid environment can be
established by lling water in a sealed vessel or chamber. After a
suciently long period, the air in the vessel is saturated by
water vapor. The humidity depends on the vapor pressure of
water, which can be tuned by dissolving a certain amount of
inorganic salts in the water (Figure 4b). Because the
uncertainties caused by ow disturbance are minimized, the
preparation of BFA lms is repeatable in each batch with a
static BF process.
Occasionally, dynamic and static BF processes yield dierent
results. For example, in a dynamic BF process, linear
polystyrene (PS) resulted in regular BFA lms only under
very specic conditions, and the formation of the BFA was very
sensitive to the polar end group, molecular weight, and casting
solvents.4144 However, in a static BF process, we have shown
that linear PS without a polar end group could also form well-
dened BFA lms under a wide range of temperatures, solution
concentrations, and molecular weights.45 These dierences may
come from the discrepancy in the evaporation rate of the
solvent or the disturbance of the gas ow. Usually, however,
both dynamic and static BF processes are ecient ways to
produce BFA lms.
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2.2. Spin-Coating and Dip-Coating
Spin-coating provides another way to control the BF process, as
shown in Figure 5a.4658 When spin-coating is employed, the
Figure 5. Preparation of BFAs by (a) spin-coating and (b) dip-coating
processes.
nucleation rate of water droplets and the inux of water
droplets into the solution become important in determining the
packing of water droplets because a large amount of the
solution dropped on the substrate is removed at the beginning
of spin-coating, and the polymer solution solidies quickly
during spin-coating. Kim et al. spin-coated cellulose acetate
butyrate (CAB) in a mixed solvent of tetrahydrofuran (THF)
and chloroform and studied the inuence of concentration on
the pore morphology.49,59 Using pure THF as the solvent, a
uniform BFA lm over a large area was obtained. Rodriguez-
Hernandez et al. prepared hierarchically micro- and nano-
structured polymer surfaces with block copolymer/homopol-
ymer blends using the spin-coating method.48 Small pores with
diameters of 100300 nm were found in the lm and were
attributed to the BF process occurring during the spin-coating
process. The pores were signicantly smaller than those formed
in conventional BF processes because the evaporation time was
much shorter for the spin-coating process (see section 3.2.3 for
details).
Dip-coating is a simple way to coat a substrate with polymer
lm, especially when the shape of the substrate is complex.6067
To perform dip-coating, a substrate is rst soaked in a polymer
solution and then removed at a certain speed, as shown in
Figure 5b. A thin layer of solution will remain on the surface of
the substrate, and after it dries, a uniform polymer lm forms
and covers the substrate. Mansouri et al. prepared BFA lms on
a nylon mesh with the dip-coating method.68 They used a
polysulfone (PSF) solution in dichloromethane and performed
the dip-coating process under high humidity to allow the
formation of a template of water droplets. A thin, robust,
porous PSF lm formed on the surface of the nylon mesh due
to the lm drainage and the BF process. Dip-coating conditions
such as withdrawal speed and holding time can be used to
control the morphology of the lm.
2.3. Generalized BF Methods
As mentioned above, in the BF process, water droplet templates
are generated by the condensation of moisture. There are
similar processes that produce ordered porous lms from a
template not involving water droplets or in which the water
droplet templates are not generated from water vapor. These
methods are called generalized BF methods. For conventional
BF methods, to prepare regular patterns, the relative humidity
of the atmosphere should be maintained at a high level.
D DOI: 10.1021/acs.chemrev.5b00069
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However, for these generalized BF methods, a high
atmospheric humidity is not required.
Water-in-oil emulsion has been used to construct porous
polymer lms.6971 The water droplets in the emulsion can
self-assemble during the evaporation of organic solvents,
yielding a hexagonally packed array. For example, Wu et al.
prepared a water-in-oil reversed hybrid microemulsion by
mixing a poly(methyl methacrylate) (PMMA) dichloromethane
solution containing P123 with a polyoxometalate (POM)
aqueous solution through shaking.69 When the microemulsion
was cast onto the substrate and allowed to dry under 3040%
relative humidity, a porous lm with an ordered pore array was
obtained. The size of the pores could be adjusted by changing
the volume fraction of water in the microemulsion, indicating
that the water droplets in the microemulsion acted as the
templates for the pores.
Similarly, porous lms can be obtained with a THF/water
mixture,49,50,7275 dichloromethane/tertiary amyl alcohol,76
dichloromethane/propylene glycol,77 or an acetone/toluene78
mixture as the solvent. The pore size will increase with the
amount of water in the solution.79 For example, Pourabbas et
al. soaked a PMMA slab in THF containing 5 or 10% water to
swell the surface of the slab.80 They then transferred the slab
into a dry atmosphere. After the solvent fully evaporated, pores
with a diameter of several micrometers were found on the
PMMA slab. The template of the pores was believed to be the
water droplet array left after THF evaporation. Because water is
the nonsolvent of PMMA, upon the evaporation of THF, the
water fraction in the solution continued to increase, leading to
phase separation between water and the PMMA solution.
These water droplets self-assembled into an ordered array and
produced hexagonally packed pores on the surface of the
PMMA slab.
Bormashenko et al. developed a novel method for preparing
porous polymeric lms with a bubble array as the template.66,81
They used a dip-coating technique to coat the substrate with a
polymer solution. The dip-coating was performed with an
unusually high pulling speed of V = 47 cm min1, and the
pulling direction was vertical. When the substrate was pulled
out of the solution, the lm was immediately dried with a hot
air current or dried nitrogen (3 m s1, 20100 C). Pores were
found on the dry lm. The authors claimed that a water droplet
array was not responsible for the formation of the porous
structure because the humidity of the gas had no eect on the
morphology of the porous lm. Instead, they proposed that
because the drying process took place at a temperature close to
or higher than the boiling point of the solvent, there should be
extensive formation of bubbles lled with the solvent vapor.
These bubbles acted as a template for the formation of pores on
the surface of the polymer lm.
3. FORMATION MECHANISM FOR BFA FILMS
In this section, the formation mechanism for BFA lms will be
discussed. It should be noted here that the formation of BFAs is
a very complicated process, and no general mechanisms have
adequately explained all experimental results. In fact, results
from dierent researchers often seem to conict with one
other,43,45,8288 adding to the diculties of revealing the
mechanism of the BF process. One important reason for this
confusing state is that the BF process is controlled by complex
heat and mass transfer, and these transfer processes are further
dependent upon various experimental parameters, including
temperature, humidity, gas ow velocity, the physical properties
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Figure 6. Formation mechanism for BFA.

of the solvents and the solution, the physical and chemical quite dierent, they all predicted that, after the solution was
properties of the solute (typically polymers), and the nature of cast, the temperature of the solution rst decreased sharply to
the substrate. Slight variation in any of the above parameters reach a minimum value and then gradually increased, as shown
can signicantly change the nal BFA lms. Moreover, there is in Figure 7.9395 It should be noted here that the substrate
no standard BF procedure, and the reported experimental
results have all been obtained using homemade equipment.
Details regarding these apparatuses, which played important
roles in BF processes, were usually not described exhaustively in
the reports. Therefore, although great eorts have been devoted
to uncovering the mechanism of the BF process, some details
remain unknown. In this section, we will summarize the results
of previous studies and give an overview of the mechanism of
BFA formation.
There have been various approaches to producing BFAs, but
the essence of all these approaches is the construction of a cold
solution surface under a humid atmosphere, under which the
moisture can condense on the cold surface. The well-accepted
mechanism of the entire BF process contains the following
steps, as shown in Figure 6: (1) cooling of the solution and
nucleation of the moisture, producing small but disordered
water droplets on the solution surface; (2) growth and self-
assembly of the water droplets, forming an ordered and closely
packed water droplet array that covers the entire surface of the
solution; and (3) evaporation of the solvent and water droplets,
leaving a hexagonal pore array on the dry lm. These steps will
be discussed in detail in the following sections.
3.1. Cooling of Solution and Nucleation of Moisture
A cold surface is crucial for the BF process. Here, cold
indicates a temperature suciently lower than the dew point of Figure 7. Temperature proles of the polymer solutions during
the atmosphere, such that water vapor can condense onto the evaporation. (a) 0.05 mL of pure chloroform evaporating in a dry
surface spontaneously. Although directly cooling the substrate environment with the substrate placed directly onto a cold plate to
and the solution by using a cold stage have occasionally been maintain the constant boundary condition. 93 Reprinted with
reported,89,90 evaporation cooling is the most widely used and permission from ref 93. Copyright 2011 Royal Society of Chemistry.
convenient method for producing a cold solution surface. (b) 0.3 mL of 1% PS (molecular weight (Mw) = 50 000) in CS2 on a
Evaporation cooling involves casting a solution with a high glass substrate with a thickness of 0.7 mm, evaporating under 60%
relative humidity.95 No gas ow was used in either experiment.
solvent evaporation rate onto a substrate. The solvent Reprinted with permission from ref 95. Copyright 2010 The Optical
immediately begins to evaporate, and the temperature of the Society.
solvent will decrease rapidly due to the enthalpy of vapor-
ization. It was reported that the temperature of a chloroform
solution fell to 06 C during evaporation,91 and for the more plays an important role in the evaporation cooling process. The
volatile CS2, the temperature could reach 6 C.92 These mass of the substrate is usually larger than that of the solution;
temperatures are signicantly lower than the dew point of the thus, the heat exchange between the solution and the substrate
atmosphere; thus, the water vapor is able to condense onto the will apparently inuence the temperature of the solution.
surface of the solution. Bormashenko and Battenbo reported that the thickness of the
Although the evaporation cooling process is easy to perform substrate could inuence the amount of condensed water by
experimentally, it is dicult to describe theoretically. Several changing the temperature of the solution, which demonstrated
researchers have conducted preliminary theoretical investiga- the importance of the substrate eect.93,96,97 Unfortunately, this
tions of the solvent cooling process and compared their results issue was usually neglected by other researchers when they tried
with the experimental data.93,94 Although their models were to discuss the eect of the substrate on the BF process.41,98102
E DOI: 10.1021/acs.chemrev.5b00069
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Nucleation of the water vapor is the rst step in the
formation of a water droplet array. As suggested by
Nepomnyashchy et al., two dierent types of nucleation may
occur: homogeneous nucleation, in which the water nucleus
appears in the gas phase near the cold liquid surface, and
heterogeneous nucleation, in which the water nucleus is formed
at the liquidgas interface as a small liquid lens.103 The
nucleation work (E) for homogeneous nucleation is
E = (P P)V + 13A13 (1)
and for heterogeneous nucleation is
E = (P P)V + 13A13 + 12A12 23R2 (2)
where P P is the pressure dierence between the nucleus
and the bulk phase, V is the volume of the spherical nucleus, ij
are the interfacial tensions, Aij are the interfacial areas between
phases i and j (water, solution, and vapor phases are referred to
as phases 1, 2, and 3, respectively), and R is the radius of the
three-phase contact line, as shown in Figure 8. From eqs 1 and
Figure 8. Simplied sketch of a liquid droplet at a liquidgas interface
used to calculate the nucleation work by Nepomnyashchy et al.103
Reprinted with permission from ref 103. Copyright 2006 American
Physical Society.
2, the free energy barriers of the two nucleation processes can
be calculated and compared. Nepomnyashchy et al. found that
the free energy barrier for heterogeneous nucleation was always
smaller than that for homogeneous nucleation.103 Therefore,
the nucleation of water droplets occurs at the liquid/gas
interface. Moreover, eq 2 demonstrates that the nucleation
work for heterogeneous nucleation is governed by interfacial
tensions. Thus, the polymers in the solutions can inuence the
nucleation because they determine the surface tension of the
solution. If the surface tension of the solution is suciently low
(or the solution is very hydrophobic), the nucleation will be
suppressed.104 Johnston et al. used poly(ethylene oxide)-b-
poly(uorooctyl methacrylate) (PEO-b-PFOMA, 2) (Scheme
2) to produce BFAs. They found that when the molecular
weight of the hydrophobic PFOMA block was increased from
70 to 140 kDa, the number of pores in the nal BFA decreased
markedly.105 A possible reason is that, with a longer PFOMA
block, the solution becomes too hydrophobic, such that the
nucleation of the water vapor is suppressed. Some other
examples of the pore density of BFA decreasing with the
hydrophobicity of the solution can be explained in a similar
way.106,107
3.2. Growth and Self-Assembly of Water Droplets
The principal feature of BFAs is the hexagonal closely packed
pores, which indicate the existence of an ordered water droplet
array on the surface of the unsolidied polymer solution. To
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Scheme 2. Chemical Structure of PEO-b-PFOMA (2)
elucidate the mechanism of the BF process, one must interpret
the growth of water droplets and the formation of the
hexagonal droplet lattice. In this section, we will briey present
the results of investigations in recent years on the growth and
self-assembly of the water droplets.
3.2.1. Shape of Water Droplets. It is necessary to
investigate the shape of the water droplets suspended on the
surface of an organic solution because the shape of the water
droplets determines the shape of the pores in the BFAs and is
related to the self-assembly process. When a small volume of
liquid is dropped onto the surface of another immiscible liquid,
it may form a droplet or spread as a thin lm. The spread
coecient S can be used to predict the behavior of the droplet
from the point of view of thermodynamics. It is dened as108
S = s (l + ls) (3)
where s and l are the surface tensions of the substrate solution
and the droplet liquid, respectively, and ls is the interfacial
tension between the liquid and the solution. For nonspread
behavior, S < 0, and for spread behavior, S 0. The surface
tension of water (72.75 mN m1) is greater than that of organic
solvents (2030 mN m1); thus, water droplets do not spread
on the surface of organic solvents. However, for organic
droplets, the situation is complicated because s and l are
comparable. A small amount of a surface-active agent may
severely change the spread behavior. For example, our group
observed that methanol droplets spread on the surface of PS
solution in CS2 because the surface tension of methanol was
not large enough to yield a negative S. However, after
polystyrene-b-poly(dimethylsiloxane) (PS-b-PDMS, 3)
(Scheme 3) was added to the PS solution, we found that
Scheme 3. Chemical Structure of PS-b-PDMS (3)
methanol formed nonspread droplets on the surface of the
solution. Thus, BFA could be prepared with a methanol droplet
array as the template.37 This phenomenon can be suciently
explained by eq 3: PS-b-PDMS signicantly decreased s,
leading to a negative S, and thus, methanol droplets did not
spread on the polymer solution.
The shape of the water droplets suspended on the surface of
the organic liquid was further investigated with microscopy.
Photographs of 10-L water droplets on the surface of paran
oil are shown in Figure 9.109 Only a small part of the droplet
can be observed when viewed from above (Figure 9a). The
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Figure 9. Shape of water droplets. (a, b) Photographs of a 10-L drop
of water deposited on the surface of paran oil observed from (a)
above the surface and (b) below the surface. (c) Sketch of the shape of
a water droplet.109 Reprinted with permission from ref 109. Copyright
1988 IOP Publishing.
radius of the three-phase line R is smaller than the radius of the
droplets r12. Therefore, to accurately measure the diameter of
the pores in BFAs, it is necessary to peel o the supercial layer
to reveal the pores underneath.110 It should be noted that water
is denser than paran oil, but the droplets are able to stay atop
the surface of the oil. This is because, for small droplets, the
strength of interfacial tensions is much greater than that of
gravity.111 Princen et al. have shown that when the droplets are
suciently small, gravity can be neglected, and the droplets are
composed of two spherical segments whose radii are
completely determined by the interfacial tensions:112
ij 2 ik 2
1+
jk jk
cos ij = 2ij
jk (4)
rij 1
=
R sin ij (5)
hij 1 cos ij
=
R sin ij (6)
where ij, rij, hij, and R are shown in Figure 9c. By changing the
surface tension of the polymer solution, one can tune the shape
of water droplets from sphere to lens.113 Note that 23 cannot
be zero; otherwise, the forces in the vertical direction will be
unbalanced. Consequently, the liquid surface near the water
droplets is curved. This curvature is the origin of the attractive
force between droplets, which will be discussed later.
Small water droplets can maintain a spherical shape because
the surface tension of water is relatively large. However, for
other liquids, the droplets may deform from spheres when they
are pressed. Our group compared the BFAs prepared under the
vapors of water, methanol, and ethanol and found that the
pores in the BFAs prepared under water vapor were nearly
spherical, whereas those in alcohol vapors were elliptical or
cylindrical with large depths and radii, as shown in Figure
10.37,39 The reason for these phenomena is that the surface
tensions of methanol and ethanol are much smaller than that of
water. When the droplets are closely packed, the growth of a
droplet is limited by the neighboring droplets. Further
increasing the volume of the droplets will lead to deformation
of the droplet, and the droplets will grow in the vertical
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Figure 10. Cylindrical pores prepared from PS-b-PDMS in methanol
vapor.39 Reprinted with permission from ref 39. Copyright 2012 Royal
Society of Chemistry.
direction. For water droplets, this deformation is dicult due to
the large surface tension, but for alcohol droplets, it is much
easier. As a result, the elliptical or cylindrical pores were
obtained under alcohol vapors.
3.2.2. Stability of Water Droplets. Two typical
morphologies are usually observed on BFA lms, as shown in
Figure 11.42 Figure 11a shows irregular packed pores with a
Figure 11. SEM images of BFAs prepared from 2 mg mL1 CS2
solutions of (a) PSBr and (b) PSNHCH2CH2OH.42 Reprinted
from ref 42. Copyright 2014 American Chemical Society.
wide size distribution, and Figure 11b shows a perfect
hexagonal lattice of monodispersed pores. It is widely accepted
that the morphology shown in Figure 11a results from the
coalescence of water droplets during the BF process.42,114,115
This coalescence is easy to understand: when two droplets
touch each other, they tend to merge.116,117 However,
experimental results show that, in most BFAs, pore arrays are
mostly regular over a larger area, as shown in Figure 11b.42 It is
dicult to imagine such uniform pores being templated from
water droplets that underwent coalescence. Thus, the water
droplets on the solution surface are quite stable; they rarely
coalesce even when they are closely packed. In other words, the
water droplets on the surface of a solution behave like a solid
ball. Thus, the rst problem when trying to elucidate the
mechanism of the BF process is how to explain the stability of
the droplets.
Several hypotheses have been proposed to explain the
stability of the water droplets. One notable phenomenon is
that, on the surface of pure oil without any solute, the water
droplets can also keep themselves from coalescing for a long
period.118 An important eect that prevents water droplets
from coalescing is the Marangoni convection caused by a
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Chemical Reviews
temperature gradient.119,120 This gradient causes convective
motion in any two droplets that suppresses their coalescence. A
thin layer of air between two water droplets may act as a
lubricant, which will also suppress the coalescence. Another
hypothesis is that the condensing water droplets are kept apart
and made to interact elastically by the vapor of the evaporating
solvent as it escapes from the surface.121 The above hypotheses
are helpful in understanding the behavior of water droplets on
another liquid surface, but they are not able to fully explain the
stability of droplets on the surface of a polymer solution. The
behavior of droplets on the surface of a solution is highly
dependent on the properties of the solute. While water droplets
on a pure chloroform surface coalesce after a certain period,
water droplets on a polymer solution surface remain stable
during the entire BF process. Thus, we can conclude that the
polymer (or other solute) in the solution must contribute to
the stability of the water droplets.
Pitois and Francois demonstrated that when the droplets
came into contact with a polymer solution, the polymer
precipitated around the droplets and formed a thin layer.122
This layer of polymer is like an envelope that can prevent water
droplets from coalescing. Direct evidence of the polymer
envelope layer was discovered on a water drop hanging on a
syringe needle in a CS2 solution of PS-b-PPP (Figure 12). The
Figure 12. Photograph of a water droplet in PS-b-PPP solution in CS2.
A solid layer at the interface between the two liquids is visible when
the solution contained in the drop is partially removed.122 Reprinted
with permission from ref 122. Copyright 1999 EDP Science, Springer-
Verlag.
concept of a protective layer is quite often invoked in the
literature to explain the formation of BFAs, and its existence is
widely accepted and believed to be the principal reason for the
stability of water droplets during the BF process. Recently, Qin
and Tang et al. directly observed the polymer lm around water
droplets during the BF process using a uorescence micro-
scope.123 They performed the BF experiments with a polymer
bearing aggregation-induced-emission (AIE) moieties (4)
(Scheme 4), which were nonluminescent when dissolved in
the solution and became highly emissive when aggregated.
Under the uorescence microscope, weakly emissive water
droplets were clearly observed after the polymer solution was
cast onto the substrate (Figure 13), suggesting that water
droplets were covered by a polymer lm. They also found that
at the early stage of the BF process, before the emissive water
droplets appeared, dark water droplets were rst observed
under a bright-eld microscope. This phenomenon indicates
that the formation of a polymeric protective lm is subsequent
to the formation of water droplets.
According to the published literature, the formation of the
polymer envelope layer is controlled by several factors. First,
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Scheme 4. Chemical Structure of Polymer Bearing AIE
Moieties (4)
Figure 13. Fluorescence microscopy images taken at (a, b) 0 s and (c,
d) 30 s after casting the solution on the substrate. Scale bar: 3 mm.123
Reprinted with permission from ref 123. Copyright 2014 Wiley-VCH.
the polymer should be insoluble in water. The precipitation of
the polymer around water droplets relies on the fact that water
is the nonsolvent for the polymer. If the polymer is too
hydrophilic, it will dissolve into the water droplets and, thus,
will not eectively protect the droplets. In this circumstance,
disordered pores such as those shown in Figure 11a are usually
found.124126 Second, the rate of polymer precipitation is also
important. Star polymers give better BFAs compared with their
linear counterparts.127,128 A possible reason is that star
polymers have higher segment density and are easy to
precipitate. Similarly, some block copolymers (BCPs) can
form starlike aggregates in the solvent and thus also precipitate
quickly around the water droplets, giving high quality
BFAs.17,129 Stenzel et al. used a light-scattering technique to
investigate the relationship between molecule aggregation and
the formation of BFAs. They found that those polymers that
could form large aggregates were able to produce better BFAs
with higher regularity.72 Moreover, if the concentration of the
polymer solution is low, the precipitation of the polymer is
slow, and the polymer protective layers around water droplets
are thin and weak. Thus, the produced BFA will be nonuniform
due to the coalescence of water droplets.42,114,115,130
In fact, solid polymer lms are not the only type of protective
layer; an interfacial adsorption layer of the solute at the water/
solution interface also eectively protects the water droplets. In
many cases, there is no evidence for the solid polymer
protective lm, but the interfacial adsorption is easy to conrm
both in theory and experimentally. Many researchers have
reported that polymers with amphiphilic molecular structure
formed ordered BFAs much more easily.131 For example,
carboxyl terminated PS could form regular BFAs, but PS
without a hydrophilic end group failed to produce regular BFA
lms under the same conditions.111 Obviously, amphiphilic
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molecules tend to assemble at the water/solution interface and
form a protective layer. The amphiphilic-molecule-protected
water droplets on the surface of a polymer solution comprise a
two-dimensional emulsion that is quite stable. If the polymer is
not amphiphilic, the water droplets can be stabilized by adding
a small amount of amphiphilic molecules into the solu-
tion.51,114,132,133 For example, Shimomura et al. demonstrated
that, with the aid of the surfactant CAP (copolymer of
dodecylacrylamide and carboxyhexylacrylamide, 5) (Scheme 5),
Scheme 5. Chemical Structure of Polymer CAP (5)
ordered BFA lms could be prepared from most liposoluble
polymer solutions.134,135 Similarly, when tetraethyl orthosilicate
(TEOS), whose hydrolysis product is also amphiphilic, was
added into PS solution, perfect BFA lms were obtained.136
These experimental results clearly demonstrate the important
function of amphiphilic molecules in the formation of BFAs.
If the interfacial adsorption occurs, the hydrophilic groups in
the amphiphilic molecules should aggregate primarily inside the
pores of the BFA. This has been conrmed by substantial
experimental results. For example, Raman spectrum mapping of
BFA lms revealed that the hydrophilic molecule or segments
were enriched in the pores.137,138 Similarly, time-of-ight
secondary ion mass spectrometry (TOF-SIMS) mapping
results also demonstrated that polar groups were primarily
located inside the pores.139141 X-ray photoelectron spectros-
copy (XPS) was also used to characterize the distribution of
elements on BFA lm.142,143 Stenzel et al. compared the
element composition of the top surface layer and the pores of a
BFA lm made from a PS-based amphiphilic BCP and found
that the content of oxygen in the pores was higher than that on
the top surface layer.142 Thus, the hydrophilic blocks were
enriched on the walls of the pores. By labeling the hydrophilic
segments with uorescent moieties, the enrichment of
hydrophilic groups inside the pores could also be directly
observed with a uorescence microscope.144,145
Another widely used method to stabilize water droplets
during the BF process is the addition of nanoparticles (NPs)
into the polymer solution. Many inorganic particles can adsorb
onto the interface of water/oil and form a mechanically strong
protective layer around the water droplets. The emulsion
stabilized by particles is called a Pickering emulsion. Some
researchers have investigated the inuence of solid particles on
the formation of polymer BFAs.146148 For example, gold NPs
were reported to be able to promote the formation of ordered
PS BFAs.147,148 The particles can be observed directly inside
the pores by SEM or transmission electron microscopy
(TEM),146,149,150 revealing that they were located at the
interface of water and the polymer solution. The properties
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of the particles, such as amphiphilicity, shape, and size, show
eects on the stability of the water droplets. The stabilization
energy E, which is dened as the energy required to remove a
particle from the interface, is given by
E = r 2(1 |cos |)2 (7)
where r is the particle radius, is the interfacial tension, and is
the contact angle (CA), as shown in Figure 14. The larger the
Figure 14. A small gold particle at the water/oil interface.151 Adapted
from ref 151. Copyright 2004 American Chemical Society.
stabilization energy, the higher the stability of the water
droplets will be and the more easily the ordered BFA can be
obtained.149,151 Judging from eq 7, the largest stabilization
energy is obtained when the CA is 90, which requires that the
particles have a balanced hydrophobicity and hydrophilicity.
For example, using amino-functionalized zeolite to stabilize
water droplets only resulted in disordered pores with varied
size, but with carboxyl-functionalized zeolite as the stabilizer,
monodispersed pores were achieved.152 The reason for this
result was that the former zeolite was too hydrophilic to
stabilize the water droplets. Other researchers have also
reported that by carefully adjusting the amphiphilicity of NPs
with a surface modication technique, better BFAs could be
obtained.153,154
3.2.3. Growth of Water Droplets. Pore size is an
important parameter of a BFA lm because many applications
depend on the average pore size. Thus, it is important to
investigate the size evaluation process for the water droplets.
The condensation of water on solid substrates has already been
investigated comprehensively.116,155158 If we assume that the
temperature of the substrate remains unchanged throughout
the growth process and further ignore the gradient near the
hemispherical droplets, we will nd that condensation on the
substrate should induce a steady-state condensation gradient of
water molecules parallel to the substrate, whose length scale can
be predicted by hydrodynamic theory. The rate of droplet
volume (V) growth is proportional to the concentration
gradient in the boundary layer, the mass diusivity, and the
saturation pressure dierence:159
dV
DpC0 1
dt (8)
where D is the diusion coecient of water molecules in carrier
gas, p is the saturation pressure dierence of water between
the environment and the surface of substrate, C0 is the
concentration of water in the carrier gas, and is the length
scale of the condensation gradient, which is related to viscosity,
the velocity of the gas ow, and D. Therefore, the growth of the
radius R of water droplets should follow a power law:
R (DpC0 1t )1/3 (9)
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Chemical Reviews
Near room temperature, the saturation pressure dierence p
is related to the temperature dierence T:
p T 0.8 (10)
Thus, the growth of water droplets is described as
R (DC0T 0.8 1t )1/3 (11)
From eq 11, we can conclude that when the concentration of
the water vapor C0, the temperature dierence, or the growth
time is increased, the average radius of the water droplets will
increase. Here, we summarize some experimental results that
can be explained well by the above equations.
A great number of researchers have reported that the size of
pores in BFAs increased with the relative humidity
(RH).43,82,110,129,160163 The RH is dened as
p
RH = 100%
ps (12)
where p is the partial pressure of water vapor and ps is the
saturated vapor pressure of water. Thus, relative humidity is
proportional to C0, and higher relative humidity will lead to a
faster growth rate. It should be noted here that relative
humidity is also dependent on the temperature, because ps
increases with temperature. Some researchers found that BFAs
obtained at higher temperature had larger pores, although the
relative humidity values were identical.87,164,165 These results
can be explained by the larger C0 at higher temperatures.
There are also some experimental results that conrm the
relationship between temperature dierences and the pore size.
The cold stage technique is valuable for these investigations
because it allows the temperature of the solution to be
controlled, whereas in the conventional BF process, the
temperature is always changing. Chen et al. reported that the
pore size in BFA was signicantly increased when the
temperature of the substrate decreased.89 Stenzel et al. also
reported similar results.90 In conventional BF processes, the
temperature of the solution is determined by evaporation
cooling and is dicult to control. A possible method for
adjusting the surface temperature is to control the evaporation
rate. For example, by reducing the environment pressure, the
evaporation process was accelerated markedly, leading to a
lower surface temperature and larger pores in the nal BFA.166
The gas velocity,90,121,129,161,167,168 the boiling point of the
solvent, 87,110,162,169174 and the solution concentra-
tion106,115,154,169,172 can also inuence the evaporation rate.
Generally speaking, a higher gas velocity, lower boiling point,
and lower solution concentration will lead to a higher
evaporation rate and lower surface temperature. However,
increasing the evaporation rate will decrease evaporation time,
which has an opposite eect on the size of water droplets.
Which factor dominates the growth process may depend on the
nature of the polymer or solvent. This may explain the
contradictory experimental results in the literature.
Substantial eorts have been devoted to investigating the
relationship between water droplet size and growth time.175180
Knobler et al. were the rst to investigate the growth rate of
water droplets on oil.109 They found that, at early times, the
average radius of the droplets R followed a power law with an
exponent of 0.3, but at a later time, the exponent became 1,
as shown in Figure 15.
The existence of two growth regimes is distinct, as shown in
Figure 15a. Figure 15b also represents the surface coverage as a
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Figure 15. (a) Average apparent diameter D and (b) apparent
surface coverage 2 of water droplets on paran oil as a function of
time. The line is simply a guide for the eye. Experimental conditions:
gas ow velocity F = 9.6 cm3 s1, T = 8.0 K, and T0 = 12.2 C.109
Reprinted with permission from ref 109. Copyright 1988 IOP
Publishing.
function of time. It should be noted that the surface coverage is
the apparent surface coverage because the observed diameter is
smaller than the diameter of the portion of the droplets beneath
the surface. Therefore, the transition time t0 is the time point
when water droplets achieve hexagonal close packing. Before t0,
the surface coverage is low, and the growth of the droplets is
controlled by the behavior of individual droplets. After t0,
droplets contact each other, and the coalescence of droplets
becomes a dominating process, thus increasing the growth rate.
In some experiments, the growth of water droplets was found
to follow a power law with an exponent between 0.3 and 1;
Knobler et al. noted that this was because the growth occurred
at the transition stage between growth of individual droplets
and coalescence-dominating growth.109 Therefore, the growth
of water droplets on liquid evolves through three stages: the
initial stage, the crossover stage, and the coalescence-dominated
stage.
Knobler et al., in their above-mentioned experiments, created
the cold surface by using nonvolatile oil and Peltier elements.
To examine the dynamics of BF formation on volatile surfaces,
Limaye et al. discarded the Peltier element and replaced the oil
with volatile benzene and chloroform.181 Thus, the con-
densation of moisture was driven by evaporation cooling. On a
benzene surface, the growth of water droplets followed the
same power law described by Knobler et al. At the initial times,
the exponent was 0.3, and at the later time, it was 0.95. On a
chloroform surface, the exponent was 0.5 during the entire
growth period. To explain the dierences between experimental
results on chloroform and benzene, the authors argued that the
surface perturbations induced by convection were important.
Chloroform evaporates faster than benzene. Thus, the
convection in chloroform is stronger and can promote the
coalescence of water droplets and increase their growth rate.181
The results demonstrate that, on a dynamic and deformable
surface such as a polymer solution, the behavior of water
droplets is more complex than it is on solid substrates.
The above growth laws were popularly invoked in the
literature to explain the growth of pore diameters in BFAs.
However, it is not safe to directly apply these conclusions to the
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Chemical Reviews
formation of BFA lms because they do not include the eects
of the polymer in the solution. Without the protection of the
polymer layer, the water droplets forming on the oil surface
tend to coalesce at high surface coverage. For the droplets on
the surface of the polymer solution, as discussed above, the
coalescence is prevented by a polymer protective layer; thus, it
is expected that there is no coalescence-dominated stage. Many
researchers have recorded the growth of water droplets on the
surface of polymer solutions.31,42,95,182 Using a light-scattering
technique, Pitois et al. found that the growth of water droplets
on the surface of PPP-b-PS solution in CS2 followed a power
law with an exponent of 0.35, a typical behavior for the growth
of individual droplets.31 As expected, they did not observe the
coalescence-dominated stage. In fact, the power law cannot
describe the entire growth process of water droplets on a
volatile polymer solution. The growth rate of water droplets is
expected to decrease and nally approach zero because both the
temperature and the viscosity of the solution will increase at the
late stage of evaporation. The real diameter growth curve
measured by Servoli et al. is shown in Figure 16.55 Fitting the
Figure 16. Data tting of experimental data points reporting the
average radius of water droplets as a function of drying time on a
poly(lactic acid) (PLA) solution in chloroform.55 Reprinted with
permission from ref 55. Copyright 2010 Elsevier.
data with eq 11 gave poor results (dashed line) due to the
existence of a plateau in the curve after 60 s. Servoli et al.
proposed a Boltzmann type equation that can better t the
experimental data:55
Rf
R= [(t t 0)/ k]
1+e (13)
where Rf is the nal average diameter of the water droplets, t0 is
the time at which R = Rf/2, and k is a parameter related to the
slope of the linear part of the diameter growth curve. However,
considering that the growth of water droplets at dierent stages
is controlled by dierent factors, eq 13 should be a
phenomenological equation; despite this, the author attempted
to give the physical explanation of the parameters.55
All the above growth laws predict that a longer growth time
will lead to larger water droplets and larger pores in the nal
BFAs; thus, changing the growth time is the most convenient
way to control the pore size of BFAs. In the BF process, water
droplets continue to grow until the temperature of the solution
rises above the dew point of the environment or the viscosity of
the solution becomes too high. Thus, the growth time is
decided by the evaporation time. Shimomura and Yan et al.
reported that the diameter of the pores in BFA was easy to
regulate by the thickness of the cast polymer solution because
the evaporation time varied with the thickness.183185 For the
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same reason, the pores in the center of the BFA lms are larger
than those near the edge of the lm because the thickness of
the solution at the center of the drop is larger.33,186
3.2.4. Assembly of Water Droplets. The nucleation of
water droplets on the surface of a polymer solution is random.
Thus, during the growth process, the water droplets oating on
the liquid surface self-assemble and nally form a closely packed
array. Marangoni convection, air ow, and the capillary eect
are believed to drive the self-assembly of water droplets. These
eects are summarized in this section.
One of the main dierences between the formation of BFs
on a solid substrate and their formation on a liquid surface is
that the water droplets on a liquid surface are moving.187,188
This motion allows the separated water droplets to collide with
each other, which enables the self-assembly of the water
droplets. Two forces are responsible for the motion of water
droplets: air ow and Marangoni convection. In a dynamic BF
process, the carrier gas ows above the polymer solution, thus
exerting forces on the water droplets along its ow direction.
Direct evidence for the interaction between gas ow and water
droplets is that the pores in the BFA deform from a spherical to
elliptical shape, as depicted in Figure 17. The long axes of the
Figure 17. SEM image of the deformed BFA caused by gas ow at the
blowing velocity of 20 m min1. The arrow indicates the direction of
gas ow.189 Reprinted with permission from ref 189. Copyright 2007
Elsevier.
elliptical pores are parallel to the direction of gas ow.189 This
suggests that the force exerted by the gas ow changes the
shape of the water droplets. Obviously, this force can also make
the droplets move on the surface of the solution. Hao et al.
found that if the humid gas ow was stopped before the
polymer solution was completely dried, the ordered packed
pores were found near the edge of the lm and no pores were
observed in the center of the lm.190 It is believed that the gas
ow carries the water droplets to the contact line and promotes
the rearrangement. However, in a static BF process, the eects
of gas ow can be neglected because no extra gas ow is
induced.
Marangoni convection (or thermocapillary convection) is
another driving force of assembly. The Marangoni eect is the
mass transfer along an interface between two uids due to a
surface tension gradient. For a drop of polymer solution on the
substrate, the evaporation rates near the contact line and near
the center of the drop are dierent. Thus, there will be a
temperature gradient on the surface of the solution caused by
the evaporation cooling. Because surface tension is dependent
on the temperature, the temperature gradient will lead to a
surface tension gradient and Marangoni convection.191 The
experimental and predicted ow eld in a drying octane drop is
shown in Figure 18.192 The velocity of the ow in the region
above the center of the vortex was measured at 7.2 mm s1.
This velocity was rather high because the contact-line radius of
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Figure 18. Flow eld in a drying octane droplet, (a) imaged

experimentally and (b) predicted.192 Reprinted from ref 192.
Copyright 2006 American Chemical Society.

the octane droplets was only 2 mm. The strong Marangoni

convection is able to drive the motion of water droplets oating
on the surface of the solution. Moreover, it is believed that
Marangoni convection can draw the water droplets into the
solution, which will yield a multilayered BFA lm.193,194 Figure 19. (a) Optical micrograph of the initial stage of water droplets
The gas ow and Marangoni convection allow the water condensation after the evaporation of toluene, showing the droplet
droplets on the surface of a polymer solution to approach each islands.43 Reprinted with permission from ref 43. Copyright 2003
other. When they are close enough, capillary interactions begin Elsevier Science. (b) SEM image of a BFA lm made of PSF. The
to play a dominant role. As discussed above, the water droplets irregular border between domains is noted with two white ellipses.197
are oating on the surface of a liquid through a subtle balance Reprinted with permission from ref 197. Copyright 2005 Elsevier.
of buoyancy, gravity, and capillary forces. The liquid surface is
curved near the water droplets. The bending of the liquid
surface can cause long-range interactions between the droplets.
With some approximations, the attractive force F between two
droplets separated by a distance l is as follows:118,195
4R6 2 1 2 0.5
2
2 1.5
F= + 0.25(1 p ) 0.75(1 p )

3l d
(14)
where R is the radius of the water droplet, = g is the specic
weight of the liquid, g is the earths gravitational acceleration,
is the density of the liquid, is the oilair surface tension, d is
the oil-to-air relative density, and p is a key parameter dened
as the ratio of the apparent droplet radius (r) above the surface
to the droplet radius (R) below the surface. Equation 14 is valid
when bond number B0 = (R/lc)2 is relatively small. Here, lc is
the capillary length dened as lc = (/)1/2. For a droplet with
a radius of 10 m, B0 is of the order 104. Thus, eq 14 can be
used to describe the interaction between water droplets on the
liquid surface. From this equation, the diameter of the water
droplets strongly inuences the attractive force (F R6), and Figure 20. Typical scattering patterns of the water droplet array during
the surface tension of the liquid is also very important (noting the process of BFA formation. (a) Island droplets with low surface
that p is also determined by surface tension). coverage. (b) Water droplets with short-range order. (c) Polycrystal.
After elucidation of the motion and interaction of water (d) Monocrystal.31 Reprinted with permission from ref 31. Copyright
droplets, the self-assembly of water droplets can be understood. 1999 Springer-Verlag.
Two other points related to the defects of BFAs are worth
noting here. First, water droplet islands form at the beginning 19b.197,198 Clear domain borders are observed in the BFA.
of assembly. As shown in Figure 19a,43 at the initial stage of These one-dimensional defects are caused by lattice mismatch
self-assembly, the water droplets form many isolated islands, when two islands merge. The second type of defect is the
and the droplets are closely packed in the islands.43,118,196 absence of pores. Han et al. claimed that this was because the
These islands expand gradually after they admit new droplets, water droplets were carried away by the vapor ow at the late
and the droplets in the islands grow larger simultaneously. stage of the evaporation.199 However, as mentioned before,
Finally, the islands touch each other and merge, producing a only a small part of the suspended droplet is above the surface
large assembly of water droplets. This process coincides with of the solution, thus making it dicult for the gas to remove the
the evolution of a light-scattering pattern in the polymer droplets. Wang et al. provided another explanation.187 They
solution.31 As shown in Figure 20, with the evaporation of believed the water droplets could completely sink into the
solvent, the scattering pattern changed from a ring to hexagonal polymer solution. Their evidence was that, under microscopy,
dots, indicating the development from islands to monocrystal- they found that one droplet surrounded by six other droplets
line water droplets. A direct consequence of such a process is suddenly disappeared but then reappeared after 0.4 s. A
the polydomain of the nal BFAs, as depicted in Figure potential explanation is that this droplet submerged into the
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polymer solution temporarily and then reemerged after a
period of time. If the submerged droplet fails to emerge before
drying of the polymer solution, a vacancy will be left in the BFA
lm.
3.3. Evaporation of Solvent and Water Droplets
With the evaporation of solvent, the viscosity of the solution
increases, and the movement of the water droplets is limited.
When the temperature of the solution is above the dew point,
the water droplets stop growing, and the evaporation of the
water droplets dominates. The evaporation process will take
several minutes. The results obtained on a quartz crystal
microbalance (QCM) revealed that, for a 1% PS solution in
chloroform, it took 2.5 min for the solvent to completely
evaporate, and another 4.5 min was needed to allow all the
water to leave the polymer lm.200 After the complete
evaporation of the water droplets, pores are left on the
polymer lm.
During the drying process, although the positions of the
droplets are not likely to change, the shape of the pores evolves.
The polymer lm plasticized by residual solvent oers sucient
uidity for the evolution of the pores. Wang et al. found that,
during the evaporation process, the apparent diameter of the
water droplets was maintained at 1.5 m for approximately 76 s
and then increased rapidly to 2.8 m in approximately 12 s. It
was believed that the polymer lm covering the water droplets
receded suddenly when they began to cure.187 Another
phenomenon worthy of mention is that, in many BFA lms,
the pores are interconnected. Obviously, these interconnected
holes between neighboring pores must appear after the solution
has suciently high viscosity. Otherwise, the droplets should
coalesce and leave a large pore. Consequently, the inter-
connected holes are generated during the solidication of the
solution due to volume shrinkage and the surface tension of the
drying solution.
The uidity of the solution during evaporation plays a
decisive role in the formation of BFAs on nonplanar substrates.
Qiao et al. investigated the preparation of BFA lms on a
curved substrate.56,128,201,202 They used several star polymers
with dierent glass transition temperatures (Tgs) to prepare
BFA arrays on a TEM grid128 and found that polymers with
Tgs higher than room temperature were unable to form
ordered BFAs. Instead, several cracks were found in the lm.
They speculated that polymers with high Tgs were rigid and
brittle and thus could not cover the curved substrate. However,
our group obtained dierent results.203 We found that a BFA
lm of PS-b-PAA (6) (Scheme 6), which has Tgs of 100 and
Scheme 6. Chemical Structure of PS-b-PAA (6)
102 C for PS and PAA, respectively, was perfectly contoured
on the TEM grid. Thus, when the surface of the polymer
solution touched the TEM grid, the solution was uid because
of the plasticization of the solvent. One piece of evidence was
that the pores on the grid were smaller than those in the mesh,
indicating that the water droplets were growing and the
solution was still deformable at that time.
M DOI: 10.1021/acs.chemrev.5b00069
Review
4. MATERIALS FOR BFA FILMS
Polymers are considered ideal materials for producing BFA
lms because (1) most soluble polymers can form robust thin
lms when their molecular weight is high enough,204 and (2)
many polymers are water immiscible and can eciently stabilize
water droplets. In the past two decades, a wide spectrum of
polymeric materials with dierent topographical morphologies
has been used to prepare BFA lms. With the development of
the BF technique, any solutes that are able to stabilize the water
droplets and form a continuous lm can be used to produce
BFA lms called nonpolymeric BFA lms. In this section, the
materials employed in the literature to prepare BFA lms and
the inuences of the structures and properties of the materials
on the formation and function of the BFAs are summarized.
4.1. Linear Block Copolymers
As discussed in section 3, linear BCPs easily form ordered BFA
lms compared with the linear homopolymers due to their
unique self-assembling behavior in solutions and at interfaces.
Many eorts have been made to investigate the self-assembly
behaviors and theories of BCPs,205213 which has promoted the
development of BF technique. At the same time, with the rapid
development of controlled radical polymerization techniques,
the synthesis of BCPs with precisely adjustable volume
fractions and chain architectures is no longer a dicult task.
Thus, several BCPs with unique structures and functions have
been prepared and used to fabricate BFA lms. Some of these
BCPs can produce regular BFAs, and some of the BCPs with
designed topology are valuable for investigating the inuence of
molecular structures on the formation of BFAs.
BCPs for BFA lms can be divided into two categories:
amphiphilic and nonamphiphilic BCPs. As discussed in section
3, nonamphiphilic BCPs will precipitate around the water
droplets, form a solid lm, and stabilize the water droplets.
However, amphiphilic BCPs can stabilize water droplets
through specic adsorption in the interface due to their surface
activity. PS-based BCPs are predominant in the available
literature because styrene is easy to polymerize via dierent
methods, and PS has good solubility in various organic solvents.
Thus, in the following paragraphs, we will rst summarize PS-
based BCPs for BFA preparation.
The rst BFA lm was prepared with a nonamphiphilic
diblock copolymer of PS-b-PPP (1) by Francois et al.17 In their
work, CS2 was used as the solvent, in which the PS block was
soluble but the PPP block was insoluble. Therefore, in the CS2
solution, PS-b-PPP chains formed quasi-spherical micelles with
an insoluble PPP core surrounded by PS arms. The authors
claimed that these star-shaped aggregates of PS-b-PPP were
crucial for the formation of BFAs because they possessed high
segment density and, consequently, could eectively protect the
condensed water droplets. Another important example of a
nonamphiphilic diblock copolymer is PS-b-PDMS (3). Our
group prepared a PS-b-PDMS BFA lm using a static
method.214 We found that a highly ordered BFA was obtained
when the concentration of PS-b-PDMS was approximately 40
mg mL1, and either higher (70 mg mL1) or lower (10 mg
mL1) concentrations resulted in irregular pore arrays.
Furthermore, the PS-b-PDMS BFA lms were converted into
a SiO2 honeycomb porous structure by pyrolysis (see section 7
for details). Recently, it was found that BCPs with PDMS
blocks could generate ordered BFAs not only in water vapor
but also in methanol and ethanol vapors. The size and shape of
pores formed in alcohol vapors were dierent from those in
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Scheme 7. Chemical Structures of Nonamphiphilic BCPs (715)

Scheme 8. Chemical Structures of Amphiphilic BCPs (1627)

water vapor.39 A detailed description is presented in section 5. butyl methacrylate) (PS-b-PnBMA, 11),218 polystyrene-b-
Other PS-based nonamphiphilic BCPs that have been used to polyuorene (PS-b-PFO, 12),219 polystyrene-b-poly(2,5-dio-
prepare BFA lms include (Scheme 7) polystyrene-b-poly- ctyloxy-phenylenevinylene) (PS-b-PPV, 13),92 PPV-b-P(S-stat-
(ethoxyethyl acrylate) (PS-b-PEEA, 7),215 polymethylene-b- C60MS) (14),220 and poly(phenylquinoline)-b-polystyrene
polystyrene (PM-b-PS, 8),216,217 polystyrene-b-poly(methyl (PPQ-b-PS, 15).221
methacrylate) (PS-b-PMMA, 9),218 polystyrene-b-poly(tert- Amphiphilic PS-based BCPs are a large class of materials for
butyl acrylate) (PS-b-PtBA, 10),101,171 polystyrene-b-poly(n- fabricating BFA lms. PS-b-PAA (6)175and its cousins (16,
N DOI: 10.1021/acs.chemrev.5b00069
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Chemical Reviews
17)142,144 (Scheme 8) are typical amphiphilic BCPs. They can
eciently stabilize water droplets during the BF process and,
thus, can produce highly regular BFAs. Hu et al. prepared PS-b-
PAA BFA lms using a dynamic BF method.82 They
systematically investigated the inuence of critical factors,
such as the concentration of the BCP solution, the relative
humidity of the atmosphere, the properties of the solvent, the
spreading volume, and the substrates, on the morphology of the
lms. They also found that the water CA of the prepared BFA
lm was determined by the porosity and the ionization degree
of PAA. Our group rst used a static BF method to prepare PS-
b-PAA BFA lms.222 We demonstrated that PS-b-PAA BFA
lms prepared with this static method had high regularity even
on nonplanar substrates.203 We also used PS-b-PAA BFA lms
to guide the growth of other inorganic materials, such as carbon
nanotubes (CNTs), ZnO, and SiO2, by mixing lipo-soluble
precursors or catalysts into the casting solution.223225 These
studies are described in section 7. Ma et al. systemically
investigated the preparation of PS-b-PAA BFA lms using a
static BF method. 110 They changed the experimental
conditions, such as the concentration of the polymer solution,
the solvent, the temperature, and, particularly, the molar ratio
of the PAA and PS segments, to control the morphology of PS-
b-PAA BFA lms. Their results demonstrated that PS-b-PAA
BFA lms could be obtained easily from CS2 or chloroform
solutions under broad experimental conditions. Moreover, with
PS-b-PAA as the dopant, a composite of PS-b-PAA and
polypyrrole (PPy) (18) was synthesized and used to prepare
BFA lms.226 Because of the introduction of conductive
polymer, the obtained BFA lms were suitable for the growth
of cultured cells, showing potential application as scaolds for
tissue engineering.
Polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP, 19)
(Scheme 8) is another widely used PS-based amphiphilic
BCP for the fabrication of BFA lms.166,227,228 For example,
Zhang et al. used PS-b-P4VP as a model polymer to investigate
the eect of a vacuum on the formation of BFAs.166 They
modied the conventional static BF process as follows: after the
polymer solution was cast on the substrate, a vacuum was
immediately applied to the chamber to achieve an appropriate
pressure. They found that, by decreasing the pressure of the
chamber, the pore size signicantly increased. This size increase
occurred because, under reduced pressure, the temperature
dierence between the solution surface and the atmosphere was
larger, leading to faster condensation of water (see section 3 for
details). Save and Billon et al. prepared PS-b-P4VP BFA lms
from a chloroform solution using a dynamic BF method.227
The pore size of the obtained BFAs was approximately 700 nm.
Because PS and PVP segments are immiscible, the authors
observed a PVP domain generated by microphase separation on
the surface of the lm. Moreover, PVP is pH-responsive
because of the reversible protonation and deprotonation of its
pyridine rings. As a result, the PS-b-P4VP BFA lms showed a
pH-responsive water CA.
Other PS-based amphiphilic BCPs include polystyrene-b-
poly(2-vinylpyridine) (PS-b-P2VP, 20),229 polystyrene-b-poly-
(ethylene oxide) (PS-b-PEO, 21),198,218 polystyrene-b-poly-
(N,N-dimethylacrylamide) (PS-b-PDMA, 22),230 polystyrene-
b-poly(N-isopropylacrylamide) (PS-b-PNIPAm, 23),231,232 pol-
ystyrene-b-poly(N,N-dimethylaminoethyl methacrylate) (PS-b-
PDMAEMA, 24),32,233 polystyrene-b-poly(2-hydroxyethyl
methacrylate) (PS-b-PHEMA, 25),143 PS-b-POTI (26),234
and dextran-b-PS (27)235 (Scheme 8). These BCPs are all
O DOI: 10.1021/acs.chemrev.5b00069
Review
reported to produce regular BFAs due to their amphiphilicity.
Recently, Russell et al. reported a unique BFA lm prepared
from PS-b-PEO.218 They cast a 70 mg mL1 cyclohexanone
solution of PS-b-PEO (21) under 85% humidity. The typical
pores in the obtained BFAs were approximately 56 nm, which
was much smaller than those in any other BFAs. The authors
noted that because the evaporation rate of cyclohexanone was
relatively slow, the condensation of water droplets was
suppressed, and only water absorption by the amphiphilic PS-
b-PEO occurred. Thus, these small pores were generated from
the swollen PEO microdomains.
Other BCPs have also been used to fabricate BFA lms. In
the following paragraphs, some typical classes of BCPs are
discussed. Poly(ethylene oxide) (PEO) and poly(ethylene
glycol) (PEG) are widely used hydrophilic chains in the
construction of amphiphilic BCPs. For example, Stenzel et al.
synthesized polystyrene-b-poly(ethylene glycol) (PS-b-PEG)
via atom transfer radical polymerization (ATRP) with a
brominated PEG chain as the macroinitiator.236 They then
converted the PS block into poly(vinyldiphenylquinoline)
(PVQ),237 which is a blue-light-emitting polymer. The authors
found that the obtained PVQ-b-PEG (28) (Scheme 9) could
Scheme 9. Chemical Structures of BCPs Containing PEO
Block (2830)
form ordered uorescent BFAs due to its amphiphilic nature.
Another PEO-based BCP for the preparation of BFA is a rod
coil polymer, PDMA-b-PEO (29), reported by Xi et al.238 It
was also synthesized via ATRP with a brominated PEO chain as
the macroinitiator. The authors compared the PDMA-b-PEO
BFA lms prepared on mica and a water surface. They found
that, for BFAs prepared on the water surface, the pores were
smaller and the regularity was lower. They attributed these
dierences to the smaller thickness of the polymer solution on
the water surface. A liquid-crystalline (LC) diblock copolymer,
poly(ethylene oxide)-b-poly(azobenzene-modied methacrylic
acid) (PEO-b-PAz, 30), was also used to prepare BFA lms by
spin-coating method.239
Fluoride BCPs are a group of unique polymers with high
thermal stability and chemical inertness and low dielectric
constants and surface energy.240 Johnston and Korgel et al.
prepared PEO-b-PFOMA (2) and used it to prepare BFA
lms.105 They found that high-quality BFAs with long-range
order could be obtained from a PEO-b-PFOMA/Freon
solution. However, because the PFOMA block was rather
hydrophobic, when the molecular weight of this block was too
large (140 kDa, with a PEO block molecular weight of 2 kDa),
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Scheme 10. Chemical Structures of Fluoride BCPs (3137)

the nucleation of water droplets was suppressed. As a result, Scheme 11. Chemical Structures of RodCoil BCPs (38
under these circumstances, the number of pores in the BFA 41)
lm was obviously small. In other examples, uoride BCPs of
polystyrene-b-poly(peruorooctyl ethyl methacrylate) (PS-b-
PFMA, 31), 241 polystyrene-b-poly(2,3,5,6-tetrauoro-4-
(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecauorodecaoxy)-
styrene) (PS-b-PFSF, 33),241 polystyrene-b-polypentauoros-
tyrene (PS-b-PFS, 33),241 PM-b-P(St-co-PFSt) (34),242 poly-
(tert-butyl acrylate)-b-poly(2-[(peruorononenyl) oxy]ethyl
methacrylate) (PtBA-b-PFNEMAs, 35), 243 PTFEMA-b-
PMMA-b-PEG-b-PMMA-b-PTFEMA (36),83,244 and poly-
(vinylideneuoride-co-hexauoropropylene) (PVDFHFP,
37)245 (Scheme 10) were synthesized and used to prepare
BFA lms with dichloromethane, chloroform, or CS2 as the
solvent. The inuences of the solvent, the molecular weight of
copolymers, the relative humidity, and the temperature on the
morphology of the BFA lms were investigated. Shimomura et
al. found that the BFA lm of BCP 35 was hydrophobic with a
water CA of 145 due to the low surface energy of the uoride
block. After peeling o the top layer of BFA lm, the obtained
pincushion structure increased the water CA to 170.246
BCPs based on conjugated blocks are of great interest due to
their unique supramolecular behaviors and photoelectric
properties. In general, these BCPs are rodcoil polymers
because the conjugated blocks are rather rigid. PS-based BCPs Some unique BCPs with functional groups were used to
of PS-b-PPP (1),17 PS-b-PFO (12),219 PS-b-PPV (13),92 PPV- prepare BFA lms. Stenzel and Davis et al. synthesized BCPs of
b-P(S-stat-C60MS) (14),220 and PS-b-PPQ (15)221 are typical PMMA-LC-b-STY-co-MAn (42) (Scheme 12), containing a
examples of such BCPs. There have been many non-PS-based side-chain LC segment and an amorphous styrene/maleic
rodcoil polymers, such as PPQ-b-PMMA (38)247 (Scheme anhydride segment.250 They compared the BFAs prepared from
11). Chen et al. synthesized a BCP containing a polyuorene BCP 42 and the LC homopolymers with a cold stage technique
block, PF-b-PSA (39), via ATRP polymerization.91 It was found and found that the BCP could yield more regular BFAs. It was
demonstrated that the BCPs formed aggregates in dichloro-
that a longer PSA block length, higher humidity, and a higher
methane because poly(STY-co-MAn) was insoluble in dichloro-
copolymer concentration created more regular BFAs. The BFA
methane. Therefore, the BCP precipitated faster around the
lms could emit blue light with a maximum light intensity water droplets and eciently stabilized them. Photochromic
between 400 and 425 nm. Furthermore, when the top layer of BCPs of spiropyran-containing polymer (43),251 photosensi-
the PF-b-PSA BFA lm was peeled o, the lm became tizer-containing BCPs of P(S-stat-VBC)-g-RB (44),252 and
superhydrophobic with a water CA of 163 0.3. Another photoreconguration BCPs of poly(4-vinylpyridine)-b-poly[6-
representative conjugated block is poly(phenylenevinylene) [4-(4-butylphenylazo)phenoxy]hexyl methacrylate] (P4VP-b-
(PPV). PPV-b-PMMA (40) has been successfully used to PAzoMA, 45)38 were synthesized and used to fabricate BFA
construct BFA lms.248 Zhai et al. also synthesized a light- lms. The BFA lms were endowed with unique optical
emitting BCP of poly(1,4-distyryl-3,5-dimenylbenzene-co-tri- properties because of the photoactive moieties.
ethylene glycol) (PDTG, 41) and successfully used it to Multiblock copolymers were also employed to prepare BFA
prepare BFA lms.249 The introduction of BFA into the lm lms.253,254 Our group investigated the formation of poly-
greatly enhanced the photoelectric conversion eciency (see styrene-b-polybutylene-b-polystyrene (SBS, 46) and polystyr-
section 7 for details). ene-b-polyisoprene-b-polystyrene (SIS, 47)255,256 (Scheme 13)
P DOI: 10.1021/acs.chemrev.5b00069
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Scheme 12. Chemical Structures of BCPs with Functional
Groups (4245)
BFA lms under static BF conditions. After cross-linking, these
lms showed improved mechanical properties and chemical
stabilities. Corresponding works will be discussed in section 6.
Another PS-based multiblock copolymer, polystyrene-b-poly-
(ethylene-ran-butylene)-b-polystyrene(PSEBS) (48),166 was
used by Zhang et al. to prepare BFA lms. Moreover, a
dierent series of poly(ether ester) thermoplastic elastomers,
such as PTMN-b-PCLDN (49), PTMN-b-PTMEGN (50), and
PTMN-b-(PCL-b-PTHF-b-PCL)DN (51), were synthesized
using dimethyl-2,6-naphthalene dicarboxylate as the hard
segment, 1,4-butanediol as the chain extender, and three
dierent soft segments of dierent molecular weights, including
polycaprolactonediol (PCLD), poly(tetramethylene ether gly-
col) (PTMEG), and polycaprolactone-b-polytetrahydrofuran-b-
polycaprolactone (PCL-b-PTHF-b-PCL).257 These polymers
were easily fabricated into regular BFA lms due to their
balanced hydrophobicity and hydrophilicity. In another
example, an anion-conducting aromatic multiblock copolymer
(QPE-b-AxBy, 52) was synthesized by a block copolyconden-
sation reaction between uorene- and phenolphthalein-

Scheme 13. Chemical Structures of Multiblock Copolymers (4652)

Q DOI: 10.1021/acs.chemrev.5b00069
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Chemical Reviews
Scheme 14. Chemical Structures of Star Polymers (5361)
containing oligomers.258 BFA lms with dierent pore sizes
were obtained by varying the humidity.
4.2. Star and Branch Polymers
Star and branch polymers are believed to be good candidates
for producing BFAs because they have high segment density
and, consequently, are easy to precipitate around water droplets
to stabilize them.19,259 For example, Stenzel and Davis et al.
prepared star homoPS polymers with 5, 8, and 18 arms using
initiators based on glucose, sucrose, and -cyclodextrin (53)
(Scheme 14) by metal-mediated radical polymerization. They
also synthesized star PS polymers with six arms (54, 55) by
reversible additionfragmentation chain transfer (RAFT)
polymerization using multifunctional derivatives of phenyl
and -cyclodextrin as the chain transfer agent.88,127 All the
obtained star PS polymers were successfully used to construct
BFA lms. They found that the formation of BFA lms was
very sensitive to the residual copper/ligand, and extensive
purication was required to ensure reproducible lm formation.
The star PS has the advantage of facile end-group
functionalization, which allows the easy production of func-
tional porous lms. The pore size, which could be altered
within the range 0.43 m, was controlled by the molecular
weight of the polymer, the number of arms, and the nature of
the end groups. This result clearly indicates that the structure at
the micrometer scale can be controlled by very small changes at
the molecular level. The blending of star polymers with linear
chains is also benecial for the BFA formation. It was
R DOI: 10.1021/acs.chemrev.5b00069
Review
demonstrated that the addition of 20 wt % of linear PS into
the star PS led to less brittle lms with fewer defects. Moreover,
many other star polymers and BCPs based on the core of C60
(56),260 phenyl (57),170 polyhedral oligomeric silsesquioxane
(POSS) (58),261 pentaerythritol (59),262 and porphyrin (60,
61)186 have been exploited as good materials for BFA lms.
Yan et al. used an amphiphilic hyperbranched polymer,
poly(amidoamine) modied with palmitoyl chloride (62)
(Scheme 15), to construct BFA lms.263 They found that the
diameter of the obtained pores was 56 m, but the depth of
the pores increased dramatically with the polymer concen-
tration. Polymer 62 is highly photoluminescent, and thus, the
obtained BFA lms could be observed under a uorescence
microscope. Importantly, the dye-loaded polymer 62 could also
form BFA lms. Thus, BFA lms with various colors were
obtained. They also synthesized hyperbranched HBPO-star-PS
(63) (Scheme 16) polymers by RAFT polymerization and used
them to construct BFA lms.185 The size of the pores could be
controlled by changing the casting volume of the solution and
the molecular weight and concentration of the polymer
solution. The authors also found that inducing pores in the
lm signicantly increased the water CA from 88 on smooth
lm to 130 on a BFA lm with a pore diameter of 3.2 m.
Yoshie et al. constructed BFAs with uorescent hyperbranched
poly(phenylenevinylene) (hypPPV, 64).193 Mono- and multi-
layers of the pores on BFA lms were obtained depending on
the thickness of the lms. Due to the conjugated structure of
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Scheme 15. Chemical Structure of Hyperbranched Polymer Scheme 16. Chemical Structures of Hyperbranched
(62) Polymers (63, 64)

PPV, the BFA lms emitted blue light under UV excitation.

Furthermore, the as-prepared BFA lms could be carbonized by
simple thermal treatment without damaging the honeycomb
structures. Tang et al. prepared a hyperbranched poly-
(tetraphenylethene) (PTPE) and used it to prepare BFA
lms.264 Depending on the obvious AIE activity of PTPE, the
BFA formation process was observed in situ under a uorescent
microscope.
4.3. Linear Homopolymers
It was initially thought that only polymers with star-shaped
architecture could generate BFA lms, whereas polymers with
linear architecture were unable to form regular patterns.
However, linear homopolymers have their own advantages of
easy synthesis and low cost. Thus, great eort has been devoted
to fabricating BFAs using linear homopolymers. Many reports
have clearly demonstrated the applicability of the BF process to The hydrophilic end group of PS plays an important role in
linear homopolymers. the formation and morphology of PS BFA lms. Wan et al.
The most widely used linear homopolymer for preparing synthesized a series of hydroxyl-end-functionalized PS (PS
BFAs is PS. PS is a commercially available plastic that is also OH) and used them to fabricate BFA lms.42 According to
easy to synthesize and modify in the lab. Thus, PS has long their results, the hydrophilic end groups could dramatically
been employed as a model polymer to investigate the improve the quality of PS BFA lms. In another report, PS with
preparation method and formation mechanism of an ionic chain end was synthesized by Billon et al.84 in a one-
BFAs.265269 For example, Limaye et al. employed PS to step reaction by nitroxide-mediated polymerization. They
examine and compare the formation of BFAs on the surfaces of prepared BFA lms with good pore regularity on a exible
two volatile liquids: benzene and chloroform.181 Analysis of the poly(vinyl chloride) (PVC) sheet or rigid PMMA plate. An
observed dramatic dierences in the pattern features revealed elegant technique based on reected and transmitted light has
that surface perturbations induced by convective noise were been used to correlate the pore sizes inside and on the top of
important for the BFA formation. Srinivasarao et al. prepared the lm. Amino-terminated PS (PSmNH2) can also produce
two-dimensional (2D) and three-dimensional (3D) ordered ordered BFAs, which may confer additional biological
BFAs with an atactic PS terminated with a carboxyl group (PS applications to the BFAs.270
COOH) by simply changing the casting solvents.121 A 3D Linear PS without any polar groups can also generate regular
network formed when benzene or toluene was the solvent, BFAs by elaborately controlling the formation conditions. Han
whereas only 2D porous lms were obtained when CS2 was the et al. investigated the inuences of molecular weight, solvent
solvent. The size of these structures could be tailored and properties, and the relative humidity of the atmosphere on the
dynamically controlled within the range 0.220 m simply by formation and pore size of PS BFAs.43 They claimed that BFAs
changing the airow velocity across the surface. formed when the solvent was toluene or chloroform, but
S DOI: 10.1021/acs.chemrev.5b00069
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Chemical Reviews
Scheme 17. Chemical Structures of Homopolymers (6571)
disordered porous structures were obtained from PS solution in
CS2. PS with an appropriate Mw was benecial for the BF
process because of the proper viscosity. In addition, in some
cases, pore arrays with rhombohedral instead of hexagonal
symmetry formed. However, our group prepared ordered BFAs
from PS solution in CS2 using a static BF process.45 Moreover,
it was found that ordered BFAs formed for a wide Mw range
from 15 000 to 214 800 and over a broad temperature range.
Recently, Shen et al. applied an electric eld to assist the
formation of BFA lms with PS271 and PS/SiO2 NPs.272 For
the PS BFA lms, the pore size decreased from 2.3 to 0.35 m
when the voltage increased from 0 to 1000 V, which was
attributed to the decrease of water surface tension under a
stronger electric eld. With the decrease of pore size, the water
CA on these PS BFA lms increased from 95 to 147. In
addition, it was reported that BFA lms could also be directly
prepared by casting a droplet of organic solvent on a PS Petri
dish.273 Further, the ordered pores were modied with
functional NPs by replacing the solvent with the NP suspension
in organic solvent.274
Other traditional homopolymers, including polystyrenesul-
fonate (65),275 PMMA (66),79,199 PVC (67),276 poly(1,2-
butadiene) (PB) (68),277,278 PDMS (69),279 and ferrocenyl-
based oligomer (70)280 (Scheme 17) can also be used to
prepare BFA lms. Peng et al. prepared regular BFAs with
linear PMMA and PMMA-crown-PMMA (71) casting from
toluene.199 Pourabbas et al. directly fabricated BFAs by casting
a mixture of solvent (THF) and a controlled amount of H2O
on a PMMA plate in a dry atmosphere aided by sonication.80
The BFAs were then decorated with hydrophobic silica NPs
grown by an in situ solgel reaction. As a result, the micronano
hierarchical surface morphology endowed the BFA lm with
superhydrophobicity.
A variety of engineering plastics, including polycarbonate
(PC, 72),60,164,281,282 poly(ether ether ketone) with Cardo
(PEK-C, 73),169,283 polyimide (PI),115,189,284 poly(phenylene
oxide) (PPO),87,174,285 PSF,197 and poly(ether sulfone)
(PESF),286 have also been employed to prepare BFA lms
(Scheme 18).
PC has good mechanical properties, high thermal and
oxidative stability, and the distinguishing optical property of a
high refractive index (n 1.6). The high refractive index makes
PC a suitable material for photonic band gap structures.
Bormashenko et al. investigated the fabrication of regular PC
BFA lms using a fast dip-coating method.282 The PC BFA lm
T DOI: 10.1021/acs.chemrev.5b00069
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Scheme 18. Chemical Structures of PC (72) and PEK-C (73)
showed optical properties typical of a 2D photonic crystal. Li et
al. systemically investigated the inuence of humidity,
concentration, temperature, and the solvent properties on the
formation of PC BFA lms.164 The results showed that highly
ordered PC BFA lms could be obtained from a chloroform or
dichloromethane solution under certain conditions. However,
BFA lm formation was not observed with THF as the solvent.
PIs are well-known engineering plastics with excellent
thermal and chemical stability. They have been used in many
areas such as microelectronics, solar cells, advanced composite
materials, and high performance bers. However, most
common PIs are insoluble in organic solvents, which limits
their use in constructing BFAs. Yabu et al. rst constructed BFA
lms with polyion complexes of polyamic acids (74, 75) and
dialkylammonium salts (76).287 After a subsequent chemical
treatment, polyamic acids were converted to PIs, and
dialkylammonium salts were removed from the BFA lm.
Simultaneously, the BFA structures were eectively preserved.
Wang et al. directly synthesized uorinated PIs of 6FDA-BDFA
(77) and 6FDA-MDA (78), which are soluble in dichloro-
methane and chloroform.189,284 The excellent rigidity and
thermal stability of PI were maintained well in these soluble
polymers. Regular BFA lms were successfully constructed with
these PIs. The size and shape of the pores could be controlled
by adjusting the solvent, concentration, humidity, and the
velocity of gas ow. Gas ow with high velocity changed the
shape of pores from circular to elliptical. Jiang et al. also
prepared BFA lms with soluble uorinated poly-
(siloxaneimide) (PSI, 79)115 and BPDA/4FMA (80)288
(Scheme 19).
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Scheme 19. Chemical Structures of PIs (7480)

PPO (81) (Scheme 20) is another type of high-performance solution concentration, and the molecular weight of PSF. Long-
thermoplastic polymer with desirable characteristics, such as term storage of the solution was necessary for the formation of
regular BFAs. This phenomenon was explained by the
Scheme 20. Chemical Structure of PPO (81) aggregation of polymer chains during storage, which was
benecial for the stability of water droplets during the BF
process. PESF (84) BFA lms were also constructed by the
conventional BF process.286 Due to the low solubility of PESF
in volatile solvent, a small amount of amphiphilic BCP (85)
(Scheme 21) was added to the casting solution to assist the
stabilization of water droplets. A dip-coating BF process was
also used to prepare BFA lms with PSF and PESF, although
good resistance to heat and water. Thus, PPO plastics are
the obtained patterns were irregular.68,291
widely studied in the eld of membrane science.289 Shi et al.
found that PPO could form BFA lms in a large range of
solution concentrations in dierent organic solvents.87,174 A Scheme 21. Chemical Structures of Engineering Plastics
special structure with large pores surrounded by small pores (8285)
was obtained when the solvent was trichloroethylene/dichloro-
methane (10/9, v/v). Reducing the environment temperature
facilitates the formation of ordered BFAs. Wang et al. observed
the formation process of BFA in a PPO/chloroform system in
situ.187 Their observation suggested that water droplets were
buried under the surface of the polymer solution during the BF
process.122 Thus, they explained that missing pores in an
ordered BFA appeared when the water droplets failed to erupt.
PSF and PESF are two types of high-performance engineer-
ing plastics with excellent resistance to heat, acid, and base. PSF
(82)197 and poly(phthalazionone ether sulfone ketone) (83)290
BFA lms were prepared by coating their solutions in
chloroform under a high humidity environment. The pore
size of BFAs could be tightly controlled by the humidity, the
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Chemical Reviews
The construction of BFA lms with conjugated polymers
such as 8699 (Scheme 22)has been thoroughly investigated
Scheme 22. Chemical Structures of Conjugated Polymers
(8699)
because of their potential applications in optical and electro-
chemical devices.20,35,292298 For example, Valiyaveettil et al.
synthesized amphiphilic poly(p-phenylene) (PPPOH, 95) by
Suzuki polycondensation and constructed BFA lms with this
conjugated polymer.293 They found that the length of the
alkoxy groups on the polymer backbone had a signicant
inuence on the formation of patterned lms. Highly ordered,
defect-free BFA lms were obtained by incorporating a 12-
carbon chain on the PPP backbone (C12PPPOH). Both the
decrease and the increase in the length of the alkoxy chain led
to the formation of irregular porous structures with defects.
Importantly, the BFA lms could emit blue light with a very
high quantum yield.
In addition, various polymer blends have been used to
construct BFAs with multifunctional and hierarchical morphol-
ogies.299305 If the blended polymers are miscible, the
composite BFA lms will have the multifunction inherited
from the component polymers. Poly(N-vinylcarbazole) (PVK)/
PS composites showed excellent processability because of the
introduction of PS and were used to prepared BFAs.306 A PVK
component endowed the composite lm with excellent
photoelectrochemical behaviors. The photocurrent of the
patterned thin lms increased with increasing PVK concen-
tration. Immiscible polymer blends can exhibit various
morphologies and properties that cannot be provided by a
single polymer.50,54,96,307,308 Han et al. employed a PS/PVP
system to prepare BFA lms.309 When the humidity was higher
than 30%, regular BFAs appeared, and the walls of pores were
mainly composed of the hydrophilic component of PVP
induced by the water droplets. This result was ascribed to the
strong hygroscopic characteristics of PVP and the strong
immiscibility of PS and PVP ( = 0.1).310 Moreover, the
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Review
morphologies of the BFA lms were reversibly stimuli-
responsive to the external environment.311 When the BFA
lm was immersed in water, PVP extruded gradually from the
pores, and the as-prepared porous structure changed into a
seaisland structure. After drying by heating, the swollen PVP
islands collapsed into pores, and the BFA structures were
recovered. Lu et al. further found that the raised height of the
PVP protrusion in the pores could be controlled by heating due
to the heating-accelerated dewetting of PVP from the PS.312 If
they pressed a patterned PDMS stamp on the composite BFA
lm when healing, various hierarchical morphologies were
obtained dependent on the temperature, the time of healing,
and the patterns of PDMS.
4.4. Biodegradable Polymers
Biodegradable polymers (Scheme 23), including PLA (100),
poly(-caprolactone) (PCL, 101), poly(lactic-co-glycolic acid)
Scheme 23. Chemical Structures of Biodegradable Polymers
(100105)
(PLGA, 102), poly(3-hydroxybutyrate) (PHB, 103),313 and
their copolymers314 and derivatives, are popular materials for
the preparation of BFA lms due to their potential applications
in bioengineering.58 However, the preparation of BFA lms
based on these polymers is dicult because the hydrophobic
ester group cannot eectively stabilize water droplets.
Shimomura et al. fabricated BFA lms using PLA and
PCL.113,315317 They added amphiphilic copolymers or
surfactants into the polymer solution to facilitate the formation
of BFA lms. Introducing polar and hydrophilic groups to the
biodegradable polymers is another eective way to promote the
formation of BFAs. For example, Chen and Ellis synthesized a
series of PLGA polymers with dierent portions of GA to
control the hydrophilicity of the copoly-
mers.89,91,94,96,174,176,179,180,318 When the molar ratio of LA to
GA was as high as 1:1, highly ordered BFA lms were obtained.
Cao et al. introduced a hydrophilic unit of L-lysine into PLA
and successfully obtained BFA lms with this modied PLA.165
Incorporation of PEG also increased the hydrophilicity of the
resulted copolymer of PEG-b-PLA (104). The diblock
copolymers with proper block ratio between PEG and PLA
produced highly ordered BFAs.319 Star and branched polymers
have been shown to contribute to the stability of the water
droplets. Accordingly, star-shaped PLA (105) was synthesized
and successfully used to construct BFA lms.130,320
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Other researchers have attempted to directly fabricate PLA Scheme 24. Chemical Structures of Cellulose-Based
BFA lms without adding surfactant or modifying the Polymers (106111)
molecular structure. Li et al. prepared ordered BFA lms
using pure PLA in THF by tightly controlling the experimental
conditions, including the molecular weight, the solution
concentration, and the humidity.163 Similarly, Servoli et al.
obtained PLA BFA lms by selecting appropriate solvents and
processing conditions. The physicochemical and kinetic factors
of the BF process have been evaluated.55 Recently, to avoid the
use of surfactants, Choi et al. presented a novel two-step
approach that involved precoating a polymer solution onto a
substrate and subsequently dipping the substrate in a binary
mixture of a solvent and a nonsolvent, generating a highly
ordered BFA lm of PLA with a large area, as shown in Figure
21.321 Chloroform and methanol were used as the solvent and

of the PEG chain illustrated the potential biological applications

Figure 21. SEM images of PLA BFA lms prepared by a two-step BF
process. (a) Low magnication with large area. (b) High magnication
with an inserted FFT pattern. (c) Tilt angle of 60.321 Reprinted with
permission from ref 321. Copyright 2014 Royal Society of Chemistry.
of the BFA lms.
Moreover, Wang et al. synthesized biodegradable amino acid
ester-substituted polyphosphazenes (PGAP, 112) (Scheme 25)
Scheme 25. Chemical Structures of PGAP (112) and UFDP
(113)

nonsolvent, respectively. The size, shape, and number density

of pores could be tightly controlled by the ratio of chloroform
to methanol.
Cellulose is one of the most abundant natural biodegradable
polymers on earth. It provides a platform for the preparation of
bioactive membranes by attaching bioactive molecules for
applications such as the detection and deactivation of bacteria.
The preparation of BFAs based on cellulose and its derivatives
is attracting increasing attention.322 The greatest diculty is
that cellulose is insoluble in most organic solvents. Kondo and
Yu et al. selected cellulose triacetate (106), which is soluble in
organic solvents, to construct BFA lms.323,324 The honeycomb
structure of the BFA lms was preserved well after
deacetylation, and thus, cellulose BFA lms were successfully
obtained. It was reported that, when assisted by CoCl2,
cellulose acetate solutions in acetone could also form regular
BFAs.325 BFA lms have also been prepared from nitrocellulose
(107) by casting its solution in amyl acetate on a cold water
surface.326
Cellulosed-based graft copolymers have also been used to
prepare BFA lms.72,88 Liu et al. synthesized three types of
cellulose graft copolymers: EC-g-PS (108), EC-g-PtBA, and
EC-g-P(PEGMA).106 However, only EC-g-PS was successfully
used to construct BFA lms due to the low aggregation level of
PtBA and P(PEGMA) chains around the water droplets. To
obtain highly ordered BFAs, a suitable polymer concentration
and side chain length and a comparably high relative humidity
were needed. By controlling the above experimental parame-
ters, the pore size could be regulated within the range 100 nm
2 m. Kadla et al. also prepared three cellulose copolymers
grafted with PEG chains (109111) (Scheme 24) terminated
with functional groups.131,327 Through a BF process, highly
ordered BFAs were obtained. The bioactive groups at the end
W DOI: 10.1021/acs.chemrev.5b00069
to prepare BFA lms, which accordingly enhanced protein
adsorption and apatite deposition in simulated body uid and
showed great advantages in promoting osteogenous dier-
entiation.328 Urushiol-formaldehyde diethylenetriamine poly-
mer (UFDP, 113), a renewable and eco-friendly biopolymer,
was also synthesized and used to fabricate BFA lms.329,330
4.5. Microgels
A microgel is an intramolecularly cross-linked macromolecule
dispersed in solution. Depending on the degree of cross-linking
and the nature of the solvent, the microgel is more or less
swollen.331 Various microgels have been used to prepare BFA
lms.332 Davis et al. reported the rst preparation of BFA lms
based on a microgel, which was synthesized using a two-step
method.333 They rst synthesized the linear prearm, (poly-
styrene)-b-(polydivinylbenzene) (PS-b-PDVB), via RAFT
polymerization. Then, the arms were coupled together via
free radical polymerization of the residual double bonds in the
polydivinylbenzene block, and the core-cross-linked star (CCS)
microgels were prepared. The cross-linking time could be used
to control the number of arms, which could reach up to 16 (on
average) per cluster. When these microgels were used to
prepare BFAs, the number and the component ratio of the
linear arms played important roles in determining the pore size
distribution and the regularity of the array. In another recent
work, Yao et al. prepared BFA lms using CCS nanogels with
the middle block P(St-alt-MAn) as the core and two side block
PS polymers as the corona.334 Poly et al. also obtained well-
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Chemical Reviews
dened BFA lms by spin-coating THF solutions of nanogels
based on poly(vinyl acetate) (PVAc).335
Qiaos group conducted a series of investigations on the
preparation of BFA lms with CCS polymers (Figure
22).56,126,128,129,201,202,336,337 For example, they reacted living,
Figure 22. Schematic illustration of the arm-rst method to synthesize
CCS polymers.
linear, low molecular weight PMMA with ethylene glycol
dimethacrylate (EGDMA, as cross-linker) and varying amounts
of methyl methacrylate (MMA, as spacer) under ATRP
conditions. A series of CCS polymers with Mn ranging from
0.3 106 to 1.0 106 and with 1174 arms were produced.
The casting conditions could be used to control the pore size of
the BFAs. In this experiment, the pore diameters increased with
humidity and decreased with ow rate. It was also found that
the pore diameters decreased with the number of PMMA arms
and the molecular weight of the star microgel.93 Qiao et al. also
synthesized CCS polymers with PDMS chains as arms
following the arm rst method and found that these polymers
could form perfect BFAs on a nonplanar substrate.202 They
believed the starlike molecular shape and low Tg were the key
factors for the formation of such BFA lms. In another paper,
they found that only those CCS polymers with Tgs less than 48
C could form ordered BFAs on a nonplanar substrate (see
section 5.2 for details).128 They also found that the end group
of the CCS polymer had an important eect on the formation
of BFAs (see section 5.6 for details).126
4.6. Nonpolymeric Materials
Nanomaterials including NPs, CNTs, and graphene possess a
variety of unique catalytic, photic, and electric properties. The
introduction of ordered patterns into these nanomaterials
usually enhances their inherent properties and leads to new
functions. In addition, inorganic materials have many other
excellent properties, such as high resistance to heat and solvent.
Therefore, the BFAs prepared with the mentioned non-
polymeric materials have attracted more and more interest
and been widely investigated.
4.6.1. Nanoparticles. Ordered assemblies of NPs are
attractive because of their unique photonic, electronic, and
catalytic properties.338,339 A variety of NPs have been used to
prepare BFAs, including NPs of metal and metal oxide and
quantum dots (QDs).340 Usually, the NPs are decorated by
organic ligands341 or polymers 151,342 to achieve good
dispersibility in organic solvents and adequate polarity for NP
adsorption at the water/solvent interface to prevent water
droplet coalescence during evaporation (see section 3.2 for
details).
The most-studied NP for BFAs is the gold NP. For example,
Korgel et al. prepared gold nanocrystals decorated with
uorooctyl methacrylate thiol (FOMA-SH) and used them to
fabricate BFA lms.151 Notably, nanocrystal BFA lms with a
long-range order at both the micrometer and nanometer length
scales were obtained, as observed in Figure 23a,b. Here, the
BFA is one level of ordered micrometer-scale structure, while a
superlattice of monodispersed gold nanocrystals forms another
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Review
Figure 23. (a, b) SEM (a) and high-resolution (HR) SEM (b) images
of a BFA lm of gold nanocrystals.151 Reprinted from ref 151.
Copyright 2004 American Chemical Society. (c, d) TEM (c) and HR
TEM (d) images of a perforated monolayer BFA lm of gold NPs
deposited on a water surface. The inset in (d) is the electron
diraction pattern of the BFA lm.347 Reprinted with permission from
ref 347. Copyright 2010 Wiley-VCH.
ordered structure at the nanometer scale. The superhydro-
phobic capping ligand provided adequate polarity and enabled
nanocrystals to adsorb at the watersolvent interface and
prevent water droplets from coalescing, which was critical for
the formation of the gold nanocrystal BFAs. This concept has
also been applied to other systems.343346 Hao et al. employed
dodecanethiol-capped gold NPs to prepare BFAs on a water
surface and obtained the perforated pore structure (Figure
23c,d).347 The prepared gold NP-based macroporous thin lms
were easily transferred onto dierent substrates for various
applications. In another study, Han et al. prepared elliptical
pores with dodecanethiol-capped gold NPs by carefully
controlling the direction and velocity of the airow.348
Other NPs have also been used to prepare BFAs, such as
various metal oxide NPs,349 Mn12 single-molecule mag-
net,350,351 PS modied clay,352 and horseradish peroxidase
(HRP) NPs.353 For example, Yonezawa et al. prepared a BFA
lm with 1H,1H,2H,2H-peruorodecanethiol (F8)-stabilized
Ag NPs.354 Sanchez et al. investigated the formation of BFA
lms with dierent NPs as building blocks, including TiO2, Co,
CdS, and SiO2.340 They found that optimum surfactants were
CnH2n+1NH4Br (n = 1214) for SiO2, CnH2n+1COOH (n = 7
11) for TiO2 and Co, and CnH2n+1SH (n = 1012) for CdS.
The C11H23COOH/TiO2-based lms maintained their honey-
comb morphologies after calcination at 500 C, and they
exhibited higher photocatalytic activity than the calcinated
nonporous lms. Moreover, a heat treatment at 110 C
provided C9H19COOH/Co particles with magnetic properties,
and an external magnetic eld was able to inuence the
formation of the C9H19COOH/Co-based BFA lm.355 In other
reports, Wu153,356 and Hao357,358 demonstrated that a POM/
surfactant complex produced in chloroform could form regular
BFA lms by a dynamic BF process or at the air/water
interface. Saito et al. prepared BFA lms using Al2O3 NPs
stabilized with a polymer containing catechol groups.359 The
lm retained its 3D structure after sintering at 600 C. The
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surfaces of the sintered BFA lms contained nanosized pores

among the NPs. Thus, they were hierarchical ordered lms and
were thermally and chemically stable. Moreover, based on the
BF technique and the interfacial assembly of porphyrin vesicles
at the interface of water/organic solution and air/water, Wang
et al. prepared ower-shaped porphyrin Janus particles with an
oriented arrangement.360 Due to the hierarchical structures, the
obtained ower-shaped particles had a multiwavelength optical
signal.
Further, Hao et al. studied the direct assembly of NPs on the
interface between BF water droplets and organic solution, and
prepared ordered uorescent rings with CdSe QDs.361 In this
process, ordered arrays of water droplets were condensed on a
chemically patterned substrate prepared by microcontact
printing (CP). Then, water droplet arrays were dip-coated Figure 24. (a) Schematic illustration for preparing complexes of s-
with an organic solution of CdSe QDs. The NPs self-assembled SWNTsCOON3C12 in chloroform and removing the lipid from the
CNT lms. (b, c) SEM images of BFA lms of SWNTs.162 Adapted
onto the interface between water droplets and organic solution, with permission from ref 162. Copyright 2007 Wiley-VCH.
and gave ring patterns after evaporation of organic solvent and
water droplets. By this process, ordered ring arrays of
NaYF4:Yb,Er NPs362 and organic molecules of oligo(p-
phenylenevinylene)s (OPVs)363 were also successfully pre-
pared. Especially, arrays of square-in-ring binary structures363
and bulls-eye-like microstructures364 were obtained by two
steps of dip-coating process. Owing to the enhanced uorescent
properties, the ordered rings can be used as sensors.363 Based
on a similar self-assembly process, Wang et al. also obtained
porphyrin rings.365 Besides, other morphologies, such as wheels
and holeshells, were also prepared by controlling the
hysteresis behaviors of substrates and solvent ratios.
4.6.2. Carbon Nanotubes and Graphene. The above
NPs are all zero-dimensional nanomaterials. In fact, one-
dimensional (1D) or 2D nanomaterials can also be made into
BFA lms. CNTs and graphene are typical 1D and 2D carbon
nanomaterials, respectively. The construction of CNTs and
graphene lms with regular porous structures has attracted
increasing interest because of their potential applications in the
areas of nanoelectronics, energy storage/conversion, and Figure 25. (a) Schematic illustration of the formation of rGO BFA
catalysis. To prepare CNT or graphene BFA lms, dissolving lm. (b) SEM and (c) TEM images of rGO BFA lm. (d) SEM image
CNTs and graphene sheets in a suitable organic solvent is the of the N-doped rGO BFA lm decorated with gold NPs by ionic
critical step. interaction. (e) Electrical behavior of GO, rGO, and N-doped rGO
Nakashima et al. used lipids to help dissolve shortened BFA lms.367Adapted with permission from ref 367. Copyright 2010
single-walled CNTs (s-SWNTs) in chloroform and successfully Wiley-VCH.
constructed BFA lms with this solution on glass and exible
poly(ethylene terephthalate) (PET) lm.162,366 After an ion-
exchange process, the lipids were removed and pure CNT BFA GO can also be transferred into the organic phase from its
lms were obtained, as shown in Figure 24. Meanwhile, the aqueous solution with the assistance of a cationic surfactant
CNT BFA lms on PET with thinner skeletons exhibited a because of the electrostatic interactions.368 Accordingly, Chen
dramatic decrease in the surface resistivity, changing from et al. prepared a complex solution of GO and dimethyl
insulating to conducting after ion exchange. CNTs are dioctadecyl ammonium (DODA) using the phase-transfer
conductive and biocompatible, and thus, the BFA lms based methods.369 BFA lms based on this complex were then
on them may have potential applications in electrochemistry prepared via an on-water spreading BF method. The as-
and tissue engineering. prepared freestanding lms exhibited superior broad-spectrum
Kim et al. grafted polymer chains on graphene oxide (GO) antibacterial activity, as conrmed using green uorescent
platelets to improve their solubility in organic solvents.367 protein labeled Pseudomonas aeruginosa PAO1 and Escherichia
Then, the modied GO was used to prepare exible BFA lms, coli (E. coli) as model pathogens. Upon decoration by TiO2
as shown in Figure 25. The pore size and the number of porous NPs, the composite BFA lm electrode showed a fast, stable,
layers were eectively controlled by the concentration of the and completely reversible photocurrent response that was
dispersion and the length of polymer chains grafted onto the approximately 2 times higher than that of the pure TiO2 lm
GO surface. Then, the GO was reduced by pyrolysis at high electrode. Wei et al. found that the complex of GO and DODA
temperature, yielding reduced GO (rGO) BFA lms. The showed interfacial activities and could adsorb at water/solution
conductivity of the BFA lms was enhanced by pyrolysis and interfaces.370 Therefore, the complexes were used as additives
N-doping, as shown in Figure 25e. to promote the formation of BFA lms of gold NPs and PS.
Y DOI: 10.1021/acs.chemrev.5b00069
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Chemical Reviews
4.6.3. Small Organic Molecules. Small organic molecules
are believed to be unsuitable for the BF process because their
crystallization during the drying process will prevent the
formation of BFAs. However, in some special cases, where the
crystallization of molecules has been suppressed, ordered BFA
lms based on small organic molecules can also be successfully
prepared. Karthaus et al. rst demonstrated that small organic
molecules could form ordered BFA lms.371 They used a
solution containing a cationic or anionic surfactant (114, 115)
and metal complex (116120) (Scheme 26) to cast the lm
and successfully obtained ordered BFAs. They speculated that
the interaction between surfactants and the metal complex
could inhibit the crystallization.
Scheme 26. Chemical Structures of Small Organic Molecules
(114120)
Another type of small molecule amenable to the BF process
are those that can form supramolecules (121131)372380
(Scheme 27). Kim et al. used 121 to produce BFA lms. 121 is
a gelator that can form organogel in chloroform.372 Thus,
during solution drying, it did not crystallize, and ordered BFAs
were successfully prepared. Jiang et al. used a ribbonlike
assembly of a small molecule, alkylated guanosine derivatives
(122, 123), to fabricate ordered BFA lms.373 These BFA lms
showed excellent capacities to encapsulate organic uorescent
dyes, which made the lms uorescent and thus allowed their
direct visualization by uorescence microscopy. Li et al.
prepared BFA lms with diphenylalanine (FF, 124) as the
raw material.374 Interestingly, it was found that 124 underwent
a hydrogen bond conguration transition from an antiparallel
sheet to a parallel sheet during the BF process, and the
aggregates were also transformed from laminar stacking to the
hexagonal structure. The authors claimed that these phenom-
ena could be attributed to the condensed water during the BF
process. The water molecules were believed to intervene in the
formation of hydrogen bonds during the self-assembly of 124
molecules. Huang et al. prepared highly ordered BFA lms with
125, benzo-21-crown-7, and dialkylammonium salt via the static
BF method.381 The reversible hostguest interaction between
the two compounds was critical for achieving suitable viscosity
and stabilizing the water droplets.
In addition, monomers and small organic molecules, which
can be polymerized or transformed into insoluble materials
during the BF process, have also been used directly to prepare
BFAs. For example, Xu et al. used an alkylcyanoacrylate (ACA,
132) solution in chloroform to prepare BFAs.102 Condensed
water droplets on the solution surface acted not only as
templates to generate pores but also as initiators triggering the
polymerization of ACA. After the evaporation of solvent and
the polymerization of monomers, polyalkylcyanoacrylate
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Review
(PACA) BFA lms were obtained. In another work, Maniglio
et al. irradiated the solution of acrylate (133, 134) and
diacrylate (135) by UV under a moist atmosphere382,383
(Scheme 28). Thus, the polymerization and fabrication of BFAs
occurred simultaneously, yielding a copolymer BFA lm.
5. MORPHOLOGICAL CONTROL OF BFA FILMS
The practical applications of BFAs are related to their
morphologies. As demonstrated above, the BF process is very
sensitive to the experimental conditions, and thus, great eorts
have been devoted to controlling the morphology of BFAs.
Many experimental variables, such as solvents, polymer
solvent interactions, substrates, the concentration of the
polymer solution, humidity, gas ow velocity, atmospheric
conditions, and solutiondroplet interactions, have been
identied as particularly crucial factors that determine the
morphologies and properties of the BFA lms. By controlling
these variables, the regularity, pore size and shape, spacing
between pores, and thickness of the membranes can be tuned
and optimized. Moreover, mechanical and optical postprocess-
ing has been used to control the morphology of BFAs. Many
unique and useful BFA lms have been prepared based on these
strategies. In this section, the control of the morphology of BFA
lms is discussed.
5.1. Solvents
Solvents used to dissolve polymers have been identied as one
of the most important factors inuencing the formation of
BFAs.81,384,385 Based on the mechanism of BFA formation,
solvents with low boiling point, high vapor pressure, and water
immiscibility are suitable for the BF process. In addition to
these inherent properties of a solvent, the interactions,
including interfacial tension between the solvent and the
water droplet55 and the thermodynamic anity between the
polymer and the solvent,87,174 have also been shown to have
obvious eects on the regularity and shape of the pores.
Therefore, the most often used solvents are CS2 and
chloroform. Other solvents, including dichloromethane,
benzene, toluene, THF, dichloroethane, xylene, and Freon,
have also been used in the BF process.20 PS serves as an
example. Ferrari et al. selected a series of solvents to assess the
inuence of the boiling point, density, miscibility, interfacial
tension with water, and thermodynamic anity with the
polymer on the formation of BFA lms.41 Their results showed
that no or poorly ordered BFAs or other morphologies were
obtained using acetone, ethyl acetate, THF, or toluene.
Chloroform, CS2, and dichloromethane allowed the formation
of regular patterns (Figure 25). These results are in agreement
with those obtained by Billon and Tian.101,174 Hansen solubility
parameters were used to quantitatively evaluate the thermody-
namic anity between PS and the solvents by Ferrari.41 They
found that only solvents with a relative energy dierence
(RED) number lower than 1 were able to generate regular
BFAs. Therefore, the boiling point, miscibility with water,
interfacial tension with water, and thermodynamic anity with
the polymer can be used as criteria to predict which solvent can
generate BFAs. However, at present, it is dicult to state which
criterion is the most important. The use of humid airow
instead of static conditions should make solvent evaporation
easier and allow BFA lms to form even when using solvents
with relatively high boiling points.121
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Scheme 27. Chemical Structures of Small Organic Molecules (121131)
5.2. Substrates
5.2.1. Materials of the Substrates. During the BF
process, the substrate or surface where the polymer solution
is deposited plays a very important role in the regularity of the
pore array in the membranes.99,101,386,387 However, it is still
unclear how and why the substrate inuences BFA formation.
Xi et al.100 and Hu et al.82 proposed that a good wettability of
solid substrates by a polymer solution beneted the periodicity
and regularity of pores based on a comparison of BFAs of the
amphiphilic copolymers PDMA-b-PEO (29) and PS-b-PAA (6)
AA
Review
on mica, glass, and silicon. Ferrari et al. believed that the surface
energy of the substrate could be an important parameter
determining the morphology of the BFAs.41 Thus, they tried to
prepare BFA lms on various inorganic and organic substrates
with a broad range of surface energies, including glass (G), glass
washed with a piranha solution (GW), silicon wafer (WSi),
glass silanized with 3-glycidoxypropyltrimethoxysilane (GWG),
glass silanized with octyltriethoxysilane (GWO), uorinated
glass (GWF), polyethylene (PE), PVC, and PET. As shown in
Figure 26, substrates with higher surface energy promoted the
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Scheme 28. Chemical Structures of Monomers (132135)
formation of long-range-ordered BFAs for the PS/chloroform
solution, but a completely opposite behavior was observed for
the PS/CS2 solution. In this case, the best results were obtained
on PVC (with a lower surface tension). In fact, the thickness,
mass, and specic heat of the solid substrate also inuence the
formation of BFA because of the various heat exchange
processes discussed in section 3.1.93 Therefore, there is no
quantitative correlation between the substrate surface energy or
wettability and the pore size and order. The combined eect of
solvent, substrate, and polymer can possibly aect the
nucleation and arrangement of water droplets.
In addition to the above solid substrates, BFAs can be
obtained on the surface of a liquid. Perforated BFAs have been
prepared on various organic solvents with high surface tension,
as discussed in section 5.8. Recently, Ma et al. found that liquid
substrates with higher surface tension and lower viscosity
produced smaller pores.83,244
5.2.2. Shape of the Substrates. Patterning a nonplanar
substrate is challenging for lithography techniques, but the
Figure 26. BFAs prepared from PS solution with various organic solvents on dierent substrates (relative humidity = 75%, 23 C, scale bar 100
m).41 Reprinted from ref 41. Copyright 2011 American Chemical Society.
AB
Review
products are of interest in many areas because they can be used
as catalysts, sensors, adsorbents, scaolds, photonic band gap
materials, and optical stop-bands. Theoretically and exper-
imentally, the formation of BFAs is not limited by the shape of
substrates, and thus, BF is a promising technique for patterning
on nonplanar substrates.
Qiao et al. rst reported the formation of BFAs on nonat
surfaces by using a solution containing a CCS polymer with
PDMS arms (Figure 27).56 This polymer has a very low Tg
Figure 27. SEM images of star PDMS BFA lms on nonplanar
substrates. (a) Spherical kaolin particle. (b) Doughnut-shaped kaolin
particle. (c) Silica chromatography particle.56 Reprinted with
permission from ref 56. Copyright 2007 Royal Society of Chemistry.
(125 C), and thus, it is soft, mobile, and able to replicate the
complex contours of substrates.388 The versatility of the system
was demonstrated by fabricating the BFA lms on a range of
inorganic particles, including chromatography-grade silica, glass
microbeads, kaolin particles, and salt or sugar crystals, which
have various shapes, sizes, and surface properties. These
structures may be useful in a range of areas, such as
chromatographic media and superhydrophobic/self-cleaning
coating. During the preparation of BFA lms on nonplanar
substrates, cracking or fracture of the lms caused by the stress
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of the curved surface is a major issue.389 Qiaos group
systemically investigated the inuence of the Tg and Youngs
modulus (E) of the polymers on the formation of cracks on the
BFA lms prepared on nonplanar substrates. They synthesized
a library of CCS polymers with dierent arm compositions,
including PDMS, poly(ethyl acrylate) (PEA), poly(methyl
acrylate) (PMA), PtBA, and PMMA, with the Tgs ranging
widely from 123 to 100 C.128 It was found that only star
polymer compositions with a Tg below 48 C could form
homogeneous BFA lms on the surface of nonplanar substrates.
In another series of -cyclodextrin (-CD)-based star polymers
with varying Tg and E, it was found that the E of a polymer was
a more important factor than Tg in determining the occurrence
of cracking during the formation of BFA on nonplanar
surfaces.390 With appropriate design, a star polymer with a
high Tg and suitable E could potentially be used to form
noncracking BFA lms on nonplanar substrates, and this
approach may ultimately lead to more and new industrial
applications of this technology.201
Recently, our group further conrmed that neither the
molecular topography nor the Tg of polymers was the key
factor in the formation of uniform BFAs on nonplanar
substrates. A linear homopolymer of PS, a BCP of PS-b-PAA,
or a commercially available triblock copolymer of SIS can be
used to produce BFA lms that perfectly replicate nonplanar
substrates (Figure 28).203,391 To explain why a brittle polymer
Figure 28. SEM images of BFAs on nonplanar substrates prepared
from (a, b) PS-b-PAA, (c) PS, and (d) SIS. (b) Magnication of
(a).203,391 Reprinted with permission from ref 203. Copyright 2012
Elsevier. Reprinted with permission from ref 391. Copyright 2010
Royal Society of Chemistry.
lm can contour the nonplanar structures, a hypothesis
involving polymer plasticization by solvent during the BF
process has been proposed. As discussed in section 3, at the late
stage of the evaporation of the solution, the polymer lm is still
deformable due to the plasticization eect of the residual
solvent. Thus, the lm is able to contour to the nonplanar
substrate without cracks.
Importantly, the morphology of BFAs on nonplanar
substrates can be used to expose the mechanism of BFA
formation. Our group investigated the formation of BFA lms
on vertical substrates.39,391 BFAs at dierent stages can be xed
onto the wall at dierent heights with the help of a capillary
force between the descending solution surface and the vertical
wall. From top to bottom, both the pore size and the degree of
order of the pore array increased (Figure 29), indicating the
evolution of the water droplet array in the whole BF process.
Gu et al. also investigated the BF process occurring on
AC
Review
Figure 29. SEM images of representative BFA lms prepared from PS-
b-PDMS on sugar particles. (bd) Magnications of the correspond-
ing areas in (a).39 Reprinted with permission from ref 39. Copyright
2012 Royal Society of Chemistry.
micropipets with a curvature gradient.392 It was found that the
BFA lms formed on the micropipets changed remarkably with
the gradually increased surface curvature. At low surface
curvatures, the pores were mostly hexagonally packed, like
those on at substrates, but at high surface curvatures, the pores
became irregularly shaped and more randomly dispersed. The
variation of the pores on the micropipet at dierent sections
was similar to that of BFAs at dierent heights on a vertical
substrate, which was valuable for investigating the mechanism
of the BF process.
5.3. Solution Concentrations
The pore size and regularity of BFAs are sensitive to the
concentration of the solution. No ordered pores can form when
the solution concentration is too low because the small amount
of solute is not able to stabilize the droplets and prevent their
coalescence.100,379,393 Additionally, sometimes the lm is so
thin that it becomes discontinuous because there is too little
solute.99,284 With the increase of the solution concentration,
water droplets can be eectively stabilized so that narrowly
dispersed pores appear. However, the increased viscosity will
weaken the convection in the solution, which is not benecial
to the self-assembly of droplets, and the pores will become
disordered when the concentration is very high.163
It has been conrmed that increasing the solution
concentration will reduce the evaporation rate of the solvent.
A lower evaporation rate has two consequences: the temper-
ature dierence between the atmosphere and the solution
surface will decrease, and the total evaporation time will
increase. As discussed in section 3, the former will result in
smaller pores, while the latter will result in larger pores. As a
result, contradictory experimental results have been reported.
In many cases, a higher concentration of polymer solution led
to smaller pores.8286 However, in some other, the pore size
did not change signicantly with the concentration of the
solution.87 Moreover, the pore size was found to increase with
the polymer concentration for some polymers.88 Therefore, the
inuence of concentration on the pore size depends on the
structure and the property of the polymers as well as the casting
condition.
5.4. Vapor Conditions
5.4.1. Water Vapor. In water vapor, high humidity is
benecial for the formation of ordered BFA
lms.160,330,394,151,296,351 No ordered pores can be generated
when the relative humidity of the environment is too low, but
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the threshold value depends on the properties of the polymer
and the additives. The more stable the water droplets, the lower
the threshold. For polymer solutions in THF, the threshold
humidity is as high as 75% for PVC (67),276 but for amphiphilic
copolymers of PS-b-PAA (6) and poly(styrene-co-acrylonitrile)
(SAN, 136) (Scheme 29), 60 and 48% humidities, respectively,
Scheme 29. Chemical Structure of SAN (136)
are sucient to enable the formation of regular BFAs.82,394 The
addition of Ag NPs into the solution of polyurethane and
PLGA (102) decreased the threshold from 90 to 30%.395 A
certain degree of control of the pore size can be achieved by
regulating humidity.82 A trend is observed where the size of the
pores in the lms increases in a nearly linear fashion with
humidity.43,163,262 However, for those materials that cannot
eciently stabilize water droplets, high humidity may result in
the coalescence of water droplets, yielding a polydisperse pore
size distribution.160
In a dynamic BF process, gas ow is used to adjust the
humidity and accelerate the solvent evaporation to create a
temperature gradient between the solution surface and the bulk
solution. Systematic investigation revealed that the presence of
the gas ow could speed the evaporation of the solvent and that
a larger temperature gradient could be achieved between the
surface of the solution and the substrate.190,396 As a result,
Marangoni convection was promoted. The convection was able
to pull the water droplets into the solution, and multilayered
pores in the BFAs formed. When the gas ow was removed, the
convection eect was suppressed, and only monolayered pores
were observed.194 Therefore, the presence of gas ow should
facilitate the formation of multiple-layered honeycomb
structures.
Although a high gas ow velocity can generate a large
temperature dierence between the solution surface and the
atmosphere and can accelerate the condensation of water vapor,
Figure 30. Schematic illustration and representative SEM images of various polymer lms prepared by the BF method in water and alcohol
atmospheres.37,39,40,401 Adapted from ref 37. Copyright 2014 American Chemical Society. Adapted with permission from ref 39. Copyright 2012
Royal Society of Chemistry. Adapted with permission from ref 40. Copyright 2009 Elsevier. Adapted with permission from ref 401. Copyright 2014
Elsevier.
AD
Review
it also reduces the total evaporation time of the solution. As
described in section 3, these two processes have opposite
eects on the pore size. As a result, while some researchers have
reported that a high gas velocity led to smaller pores,121,161,167
others reported opposite results.168 In addition, the gas ow
was also able to distort the water droplets.189 When the casting
was performed at high gas velocities (>60 m min1) with a
horizontally tilted nozzle, the BFA pores were not spherically
shaped and hexagonally ordered but were elliptically distorted
and showed more of a brick-wall-type rectangular arrangement.
5.4.2. Nonaqueous Vapors. Usually, the BF process is
performed in a water vapor atmosphere, and thus, the
condensed water droplets on the surface of the solution act
as templates to produce pores. For most of the polymers,
ordered BFAs can be obtained in water vapor in suitable
conditions (Figure 30a). Besides water, other vapors can also
form BFs under the right conditions.397,398 However, the
inuence of the type of vapor atmosphere on the formation and
morphology of pores has long been neglected by most
researchers. Only a few publications discuss the preparation
of BFAs in nonaqueous vapor.399401 The morphologies of
BFA lms prepared under nonaqueous vapor are summarized
in Figure 30. Disordered shallow holes with very large size
(Figure 30b) or nonuniform spheres (Figure 30c) were found
after casting a polymer solution in an ethanol or methanol
atmosphere, an eect that could be attributed to the low surface
tension of alcohols. Condensed alcohol spreads but does not
form stable droplets on the surface of the polymer solution. If
alcohol cannot dissolve in the polymer solution, such as
methanol in a PS solution of CS2, a at lm with very large
holes will be obtained. Otherwise, if alcohol is miscible with the
solvent of the polymer solution, nonuniform spheres will be
produced in a process similar to the nonsolvent induced phase
separation because the alcohol acts as the nonsolvent.402 When
mixed solvents of water and alcohol were used as the
atmosphere, with the increase of the fraction of alcohol, the
morphologies of the obtained lms showed a conversion from
porous lms to spherical segments and microspheres.
Recently, our group prepared BFAs with PS-b-PDMS (3) in
methanol and ethanol vapor and systematically investigated the
inuence of the atmosphere on the morphology of the BFAs,
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including the shape, size, and regularity of the pores.39 With the
decrease of the surface tension and evaporation enthalpy of the
atmospheric solvent, the volume of the pores increased, and the
shape of the pores changed from spheroid to ellipsoid and
cylindrical (Figure 30e,g). This is the rst report of a successful
preparation of ordered polymeric BFA lms under a non-
aqueous atmosphere. The formation of ordered BFAs in
alcohol vapors can be ascribed to the preferential aggregation of
low-surface-energy siloxane segments of PS-b-PDMS at the air/
solution interface, thus preventing the spread of CS2-saturated
methanol droplets. Based on the results, a universal modied
BF process was devised for preparing BFAs in methanol vapor
with conventional polymers by adding a small amount of a
surface-active agent, such as siloxane- and uorine-containing
BCPs, to the casting solution.37 The pores in the PS lms
prepared with this method were cylindrical with large depth
diameter aspect ratios (Figure 30d), and the diameter and
depth of the pores could be easily controlled by the
experimental conditions.
5.5. Interfacial Tension between Water Droplets and the
Polymer Solution
Because of the inherent mechanism of utilizing water droplets
as the templates of pores in BFAs, the interfacial interaction
between water droplets and the solution plays an important
role in the morphology of BFAs.55 The interfacial tension Figure 31. SEM images of BFA lms prepared from a CCS polymer
between water droplets and the polymer solution is decided by with various end groups. The insets are the chemical structures of the
end groups: (a) acetonide; (b) hydroxyl; (c) peruoroalkyl.126
both the solvent and the solute of the solution. Therefore,
Reprinted with permission from ref 126. Copyright 2008 Wiley-VCH.
changing the hydrophilicity of the polymers and adding
surfactants to the solution can modulate the interfacial tension.
Using small molecule surfactants or hydrophilic polymers as
Changing end groups can modify the hydrophilicity of
additives is also an eective way to control the morphologies of
polymers, and a suitable hydrophilicity is needed for the
BFA lms owing to the decrease of the interfacial tension
formation of highly ordered BFAs. Qiao et al. systematically
between the polymer solution and the water droplets.405
investigated the manipulation of lm features by controlling the
Shimomura et al. added various surfactants with dierent
polymer end groups.126 They rst synthesized the star polymers
hydrophilelipophile balance (HLB) values into the PLA
end-functionalized with acetonide-protected dendrons (gen-
solution for the BF process.113 They found that, with the
erations 14) via the arm rst method. Deprotecting the
increase of the HLB value, the morphology of the casting lm
acetonide groups yielded hydroxyl-functionalized CCS poly-
changed from highly ordered arrays with spherical pores to
mers, and modifying these hydroxyl groups with pentadeca-
disordered arrays with ellipsoid pores. Further increasing the
uorooctanoyl chloride gave a third series of functionalized HLB value caused the disappearance of pores (Figure 32ac).
CCS polymers. When these CCS polymers were used to Wan et al. also controlled the pore shape by adding hydrophilic
prepare BFAs, the authors found that the morphologies of the
BFAs were dramatically dierent (Figure 31). The CCS
polymers with amphiphilic character (with hydrophilic end
groups) aorded interconnected porous morphologies with
multiple layers of pores, whereas the CCS polymers with
pentadecauorooctanoyl end groups showed highly ordered
monolayers of cylindrical pores with extremely thin walls. This
work provided a possible method for tuning the morphology of
BFAs. These results agree well with those reported by Wan et
al.,186 who used porphyrin-core star polymers with PS arms
(60) and PS-b-PHEMA (61) arms to construct BFA lms.
Monolayers of highly ordered pores and multilayers of pores
were generated from star PS and star PS-b-PHEMA,
respectively. The small amount of hydrophilic HEMA units Figure 32. SEM images of BFA lms with various surfactants and
had a signicant inuence on the morphology of the BFA. hydrophilic polymers. (ac) PLA lms with assistance of (a)
Linear PS with dierent hydrophilic end groups, including dioleoylphosphatidyl ethanolamine (DOPE), (b) dioleoylphosphatidyl
bromo, hydroxyl, sodium carboxylate, ethanolamine, diethanol choline (DOPC), and (c) dilauroylphosphatidyl choline (DLPC).
HLB value: DOPE < DOPC < DLPC.113 Adapted with permission
amine, 2-amino-1,3-propanediol, and 2-(2-aminoethoxy)- from ref 113. Copyright 2009 Royal Society of Chemistry. (d, e) PS
ethanol, showed similar results.42,403 For PS-b-PDMAEMA, lms prepared from a chloroform solution without (d) and with (e)
only block copolymers with appropriate block ratios obtained PDMAEMA (7 mg mL1). (f) PS lms prepared from a THF solution
ordered BFAs because of the suitable interface tension between with 4 mg mL1 PDMAEMA. The insets are cross-section views.406
copolymer solution and water droplets.404 Adapted from ref 406. Copyright 2011 American Chemical Society.

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Figure 33. (a) Schematic illustration of shrinking of BFA lms using a thermally shrinkable substrate. (bi) SEM images of PB BFA lms before (b,
c) and after (di) shrinking. The shrinking directions are shown in (c).277 Adapted with permission from ref 277. Copyright 2008 Wiley-VCH.

polymer into a PS solution.406 When chloroform was used as Recently, our group developed a noncontact photomanipu-
the solvent, with the increase of the amount of poly(N,N- lation technique to modulate the shape of the pores in BFA
dimethylaminoethyl methacrylate) (PDMAEMA), the pores lms made of an azobenzene-containing polymer of P4VP-b-
were changed from near-spherical to ellipsoid in shape (Figure PAzoMA (45).38 This technique is based on the mass
32d,e). However, when THF was used as the solvent, ellipsoid migration caused by the photoreconguration of azobenzene
pores were always obtained regardless of the amount of units in the azobenzene-containing polymers. It allows
hydrophilic polymers due to the low interfacial tension between nanoscopic elements of materials to be precisely manipulated
water droplets and the polymer solution in THF (Figure 32f). with good reproducibility and high throughput, and it causes
Recently, they also reported an easy and eective method for massive motion at the micro scale (Figure 34a).407 Under the
manipulating the pore size of BFAs by adding various amounts
of amphiphilic BCPs into the solution of PS with long alkyl or
uorinated end groups.114
5.6. Deformation of BFA Films
Usually, the pores obtained by the BF process are circular.
However, pores with other shapes are expected in many special
applications. Therefore, a variety of physical secondary
processes have been used to create novel BFAs with
nonconventional pores. Both mechanical stretching and
shrinking can transform hexagonally arranged round pores.
For example, Shimomura et al. demonstrated that when a BFA
lm of PCL, a viscoelastic polymer, was mechanically stretched,
the isotropic array of hexagonal pores was transformed into an
anisotropic alignment of stretched pores.315 Geometric patterns
observed on the stretched lm were elongated hexagons,
rectangles, squares, and triangles, depending on the stretching
direction. The arrays of stretched pores could guide the
spreading of cardiac myocytes along the long axis of the pores.
Shrinking is also able to control the shapes and sizes of the
pores. The same group also illustrated the topological changes
in BFA lms on a thermally shrinkable substrate, as shown in Figure 34. Schematic and SEM images of the photoreconguration of
P4VP-b-PAzoMA copolymer BFA lm. (a) Schematic illustration of
Figure 33a.277 After thermal shrinking, porous lms with the transition movement of azobenzene. (b) Two types of irradiation
various geometrical patterns (ellipsoids, rectangles, and with dierent types of polarization light (S and V). (c, d) SEM images
triangles) were fabricated (Figure 33bi). The sizes of the of BFA lm after irradiation along the S and V directions for 30 min,
pits were reduced from several micrometers to hundreds of respectively.38 Reprinted with permission from ref 38. Copyright 2014
nanometers by repeated cycles of thermal shrinking. Wiley-VCH.

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Figure 35. (a) Calculated curves of dierential pressure and critical dierential pressure vs the radius. Insets are pore structures of ordered
membranes prepared from solutions using benzene, chloroform, and CS2 (from left to right) as the solvent and an illustration of the formation of
perforated pores.409 (b) Illustration of the formation of BFA lms with perforated pores on a glass surface.255 (cf) SEM images of the typical BFA
lm with perforated pores prepared on an ice surface (c, d)409 and glass substrate (e, f).255 Adapted from ref 409. Copyright 2011 American
Chemical Society. Adapted from ref 255. Copyright 2012 American Chemical Society.

irradiation of linearly polarized light, circular pores in the BFAs
were converted into rectangles, rhombuses, and parallelograms
in 30 min, depending on the polarization direction of incident
light (Figure 34bd). After a secondary irradiation by rotating
the sample 90, the transformed circular pores were recovered,
demonstrating good reversibility for this photodeformation
process.
5.7. Strategies for Perforated BFAs
Polymer lms with uniform perforation can act as separation
membranes and masks. In most studies, there is always a
bottom layer under the pores of BFA lms, and thus, the pores
cannot perforate the lm. Shimomura and Parisi et al. prepared
freestanding perforated BFA lms by depositing a dilute
solution of an amphiphilic polymer (5) and nitrocellulose
(107) on the surface of water.326,408 This method is called on-
water spreading. Wan et al. demonstrated that the surface
tension of soft substrate was essential for the formation of
perforated BFAs.409 They proposed that, with the evaporation
of the casting solvent, the thickness of the polymer solution
became thinner than the diameter of the water droplets.
Consequently, a meniscus formed under the water droplet,
where the water droplets and the substrate liquid were
separated by a thin polymer lm (Figure 35a). The pressure
dierence induced by the surface tension of the substrate liquid
across the meniscus during the evaporation of water droplets
should exceed the critical pressure at which the thin polymer
lm ruptures, generating perforated pores (Figure 35c,d).
Therefore, perforated pores could form on the surfaces of
glycerol and formic acid with high surface tension but not on
those with low surface tension, such as acetic acid, TEOS, ethyl
acetate, ethanol, isopropanol, and methanol. Furthermore, Hao
et al. prepared highly ordered freestanding BFA lms with
asymmetric perforated pore structures from PS/dodecanethiol-
stabilized gold NPs at an air/ice interface.410 Because there was
AG
a very thin water lm on the melted ice surface, the condensed
water droplets on top could run through the solution and
contact the water lm underneath, forming perforations during
the BF process. Based on these ndings, perforated BFA lms
of brominated PEO, miktoarm star copolymers and cellulose
triacetate were obtained on ice substrates.171,324,411
Goedel et al. fabricated microsieves with a hierarchical
porous structure by creating BFA lms on a structured
substrate.412 Usually, the structured substrates were made of
a layer of spherical glass beads protruding out of a planar
surface or plates structured via embossing, engraving, or
etching. During the BF process, water droplets partially
penetrated into the layer and created pores in the nal solid
polymer layer. The trenches of the structured substrate were
lled with polymer at a level much deeper than the penetration
depth of the water droplets. After the separation of the vitried
layer from the substrate, thin polymer membranes were
obtained with a hierarchical structure consisting of an ultrathin
active separation layer with submicrometer pores and a
supporting layer with larger pores.
Recently, our group also developed a versatile method to
prepare perforated BFA lms on solid substrates.255 The key
step of this method is to rapidly aspirate the excess solution
underneath the oating droplets array during the evaporation
process (Figure 30b). With the descent of the solution surface,
the oating droplets touched the substrate, only separated by a
thin layer of polymer. The thin interfacial polymer layer
ruptured from the pressure between the water droplet and the
substrate. As a result, the water droplets adhered to the
substrate, and perforated pore structures appeared after the
complete evaporation of the solvent and water, as shown in
Figure 30e,f.
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5.8. Methods for Hierarchical BFA Films
Hierarchical structures of materials are necessary for many
device applications. For BFA lms, the hexagonal BFAs make
up one level of the hierarchical structures, and another level can
be either a smaller scale structure induced by microphase
separation413 or a larger scale patterns generated by external
masks or substrates.414 Besides, multilevel BFA lms can be
produced by two steps of spraying atomized water droplets.415
Hayakawa and Horiuchi et al. synthesized a semi-rodcoil
BCP of PS-b-POTI (26) containing mesogenic oligothiophene
on side chains.234 After casting the polymer solution under a
moist atmosphere, a lm with hierarchical structures of three
tiers from angstroms to micrometers was obtained: a liquid
crystal phase and phase-separated nanodomain structures
formed by BCPs and ordered BFAs (Figure 36ac).
Figure 36. Hierarchically self-organized BFAs. (ac) BFA lm made
from semi-rodcoil BCP PS-b-POTI. (a) SEM image of hierarchical
BFA lm. (b) TEM image of the corresponding areas in (a). (c)
Corresponding sulfur-distribution image.234 Adapted with permission
from ref 234. Copyright 2003 Wiley-VCH. (dg) BFA lms made
from a blend of PS and triblock copolymers of PS5F-b-PS-b-PPEGMA.
(d, e) Atomic force microscopy (AFM) topograph images of BFA
lms (d) before and (e) after annealing. (f, g) Corresponding AFM
phase images of the holes.48 Reprinted from ref 48. Copyright 2009
American Chemical Society.
Rodriguez-Hernandez et al. reported the preparation of
hierarchically micro- and nanostructured polymer lms with
blends of poly(2,3,4,5,6-pentauorostyrene)-b-polystyrene-b-
poly[poly(ethylene glycol) methyl ether methacrylate] (PS5F-
b-PS-b-PPEGMA, 137)/PS48,416 (Scheme 30). The interplay of
the formation of BFAs and the self-assembly of the triblock
copolymer allowed the preparation of polymer lms with
micrometer-sized pores decorated with nanostructured BCPs.
The chemical composition of the surface could be varied by a
surface rearrangement upon annealing in either dry or humid
air (Figure 36dg), and the porous nanostructure could be
modulated from a micellar array to a lamellar phase when the
lm was exposed either to air or to THF vapor. Russell et al.
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Review
Scheme 30. Chemical Structure of PS5F-b-PS-b-PPEGMA
(137)
prepared BFA lms with PS-b-PnBMA (11) to construct
regular micrometer-scale pores and degraded the component of
PnBMA by UV irradiation to produce nanoscale pores. Thus, a
multilength scale porous polymer lm was obtained.218
Additionally, Schubert et al. demonstrated a hierarchically
porous lm via a surfactant-assisted BF process.417 They added
a prehydrolyzed silica sol containing the nonionic surfactant to
the casting solution. Thus, during the BF process, water
droplets produced regular macropores, and the surfactant self-
assembly induced the microphase separation at the nanometer
scale. After removing organics at high temperature, micro-,
meso-, and macroporous SiO2 was obtained. The pores were
not strictly ordered; however, the poor regularity had no
inuence on the adsorption applications. Sel et al. used the
surfactant-assisted BF process to prepare BFA lms of PVDF
HFP (37) and silica sol.245 Subsequently, the surfactant was
removed by Soxhlet extraction, and organicinorganic lms
with hierarchical structures of macro- and mesopores were
obtained. After introducing SO3H into the silica particles, the
prepared lms showed high proton conductivity owing to the
hierarchical porous structures. In another example, Saito et al.
prepared BFA lms with NPs of SiO2, TiO2, Al2O3, and ZnO
stabilized by mussel-inspired copolymers.349 After removing the
polymers by calcination at a high temperature, mesopores were
produced among the NPs. Therefore, hierarchical porous
organic lms were produced.
The hierarchically ordered BFA lms were also prepared with
the assistance of masks or patterned substrates. Kim et al.
prepared diverse hierarchical structures by placing a grating-
type mask on the polymer solution during the BF process,
physically conning the nucleation and the growth of water
droplets.198 After evaporation was complete, the grating
structure itself and the hexagonally packed pores constituted
independent multiscaled orderings in the polymer lm (Figure
37a,b). Kim et al. reported the combination of top-down and
bottom-up approaches to produce dual-patterned honeycomb
lines.372 They rst prepared a BFA lm with a photoresponsive
small molecule (121) and then patterned the lm by exposing
it to UV irradiation through a photomask, inducing selective
chemical cross-linking in the exposed region. After removing
the non-cross-linked polymer with organic solvent, honeycomb
lines were obtained at predened locations (Figure 37c,d).
Qiao et al. also used the combined method of BF and
photolithography to prepare hierarchical BFAs using a photo-
cross-linkable polymer of star PMA terminated with 9-
anthracene.201 Based on the reversible cross-linking reaction
of anthracene under UV irradiation, dierent patterns could be
generated on BFA lms by photolithography. Moreover,
hierarchical BFA lms can be produced by using patterned
substrates, such as a TEM grid, as mentioned in section 5.2.
Therefore, the combination of the BF process, patterned
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Figure 37. SEM images of well-ordered hierarchical BFA structures.
(a, b) Using a parallel grating (a) before and (b) after the nucleation of
water droplets.198 Reprinted with permission from ref 198. Copyright
2007 Wiley-VCH. (c, d) BFA lines prepared by UV lithography. (d)
Thinnest lines achieved by UV lithography.372 Reprinted with
permission from ref 372. Copyright 2009 Wiley-VCH.
substrates, and photolithography with masks can create
hierarchical porous polymer lms with three or more levels,
and these have great application potential.201
5.9. Large-Scale Preparation of BFA Films
The high-throughput and large-scale preparation of ordered
BFAs is still a tough task since the rst publication of BFA lms
by Francois two decades ago.17 This is why their commercial
application is hardly reported. Recently, two breakthroughs
have been achieved, and are expected to promote the
industrialization of the BFA lms.
The rst strategy involving a two-step process without the
addition of the surfactants was developed by Bui et al.321,418
First, the polymer solution was coated on a solid substrate to
fabricate a large-scale thin polymer lm with a uniform
thickness. Then the lm was dip-coated with a mixture of a
Figure 38. (a) Preparation of BFA lms with large areas. (bd) SEM images of the PMMA BFA lms prepared with chloroform/methanol (85/15,
v/v) under a relative humidity of 55% and a temperature of 23 C. The inset in (b) is the FFT pattern. The inset in (c) is the patterned pincushion
lm. (e, f) Two-dimensional and 3D AFM images, respectively, and (g) cross-sectional prole of (e). The red line in (e) indicates the location of the
cross-sectional prole.418 Reprinted from ref 418. Copyright 2015 American Chemical Society.
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highly volatile solvent and a nonsolvent followed by exposure
to ambient air, as shown in Figure 38a. The evaporation of the
mixture under ambient air eventually induced phase separation
and spontaneously created a highly ordered honeycomb
micropattern on the thin polymer lm, as shown in Figure
38bg. The pore size of the patterned lm could be further
ne-tuned through modulating the experimental conditions
such as nonsolvent content, ambient humidity, and evaporation
temperature. Patterned lm was observed throughout the
coated surface, as large as 150 cm2. The advantages of the newly
developed strategy over the conventional BF approaches rely
on that the nonsolvent (usually methanol) can induce the
transport of the polymer to stabilize the droplets, and enhance
the lateral capillary force between the adjacent droplets,
promoting the formation of the ordered structures. By this
strategy, large areas of highly ordered porous lms of PMMA
and PLA that are dicult to prepare using conventional BF
methods have been successfully obtained.
The other strategy was devised by Yamazaki et al. in Fuji
Film Co.18,419,420 They examined the formation mechanisms of
the line defects in BFA, and claried two types of formation
mechanisms of the divergent mode line defects and the
convergent mode line defects caused by the tectonics of the
water droplet arrays. The calculation indicated that an optimum
water droplet growth time was necessary for the formation of
defect-free polymer lm. An experimental apparatus shown in
Figure 39a was designed based on the theory, and A4-sized
defect-free BFA polymer lms (Figure 39b) were fabricated on
this apparatus. A European patent was also applied by Fuji Film
Co. to protect this new bottom-up microfabrication techni-
que.18 More industrial application information can be found on
the Web site of Fuji Film Co.421
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Figure 39. (a) Schematic illustration of the experimental apparatus.
(b) Photograph of a defect-free BFA lm prepared on an A4-sized
PET lm. The inset image shows a laser diraction pattern of the BFA
lm.419 Adapted with permission from ref 419. Copyright 2013 Royal
Society of Chemistry.
5.10. Other Methods
As discussed in section 3, the attraction between water droplets
comes from interfacial tension, and their repulsion is caused by
the slight deformation of water droplets when they touch.
Therefore, the pores in BFAs are usually packed closely, as
Figure 40. BFA lm with non closely packed (NCP) pores. (a, b) SEM (a) and AFM (b) images of the closely packed BFAs prepared without a
heating stage. (c) Illustration of the formation of transition-type morphologies. (dg) SEM images of corresponding BFA areas in (c).422 Adapted
with permission from ref 422. Copyright 2013 Royal Society of Chemistry.
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shown in Figure 40a,b. Chin et al. developed a novel method to
control the separation between pores and to prepare non
closely packed arrays of micrometer and submicrometer
pores.422 When water droplet arrays formed on the surface of
the polymer solution, the authors began to heat the substrate
and the solution to a temperature above the dew point (Figure
40c). This caused rapid evaporation of both the solvent and the
water droplets. The water droplets quickly became immobilized
due to the increasing viscosity of the solution, but the solution
remained deformable. As a result, the pores on the surface
continued to shrink along with the water droplets, as shown in
Figure 40dg. With this method, the authors prepared BFAs
with feature separation-to-size ratios of up to 12.44.
Porous bers423426 and microspheres427 have been prepared
by combining the BF technique with other methods. For
example, Li et al. developed a simple method called
nonsolvent assisted electrospraying to prepare hierarchically
porous polymer microspheres, as shown in Figure 41a.428 A
PMMA solution in mixed solvents of dichloromethane
(solvent) and hexanol (nonsolvent) was electrosprayed, and
the formed microdroplets were deposited onto a substrate.
After drying the solvents, the porous microspheres were
obtained, as shown in Figure 41b,c. Nonsolvent-induced phase
separation and the BF process were responsible for the
formation of the hierarchical porous structures. The nonsolvent
not only induced phase separation but also stabilized the
interface between the droplet and the air, thus preventing the
droplet from undergoing strong deformation. Therefore, the
nonsolvent was benecial to the formation of regular and
uniform microspheres. The hierarchically porous microsphere
signicantly increased the surface roughness and, consequently,
the hydrophobicity; thus, the CA could become as high as
152.2. Cho et al. prepared porous microspheres with a
nonsolvent-assisted microuid method.429 Briey, an oil phase
droplet, which was composed of PLGA (102), 2-methylpentane
(PCM, nonsolvent), and dichloromethane (solvent), was
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Figure 41. (a) Schematic illustration of porous microspheres prepared
by combined BF and electrospraying processes. (b, c) SEM images of
porous microspheres prepared with dierent ow rates: (b) 2 and (c)
3 mL h1. Insets are magnied SEM and TEM images.428 Adapted
with permission from ref 428. Copyright 2013 Royal Society of
Chemistry.
discontinuously introduced into a 1 wt % poly(vinyl alcohol)
(PVA) aqueous solution that owed continuously throughout
the tube-type uidic apparatus. After solidication, porous
microspheres with a surface dimple pattern were obtained. The
surface dimples were demonstrated to be replicas of PCM
droplets that underwent a similar process as in BF, whereas the
internal pores contributed to the nonsolvent-induced phase
separation. The particle size can be well controlled by the ow
rate of the PVA aqueous solution, and the size of the surface
dimples can be adjusted by the ratio between PLGA and PCM.
Other microporous polymer microspheres, such as PS, PMMA,
PLA, and PCL, have also been prepared by this method.
Zhang Newby et al. developed a modied BF approach to
prepare a porous polymer lm with dierent surface
features.430,431 As shown in Figure 42ad, they rst produced
an ordered water droplet array on a SiOx or Si substrate by
drying pure ethanol in a humid air ow. During the evaporation
of ethanol, water condensed on the ethanol surface and
accumulated near the receding contact line. This induced the
formation of water ngers at the receding contact line and
consequently ordered arrays of water droplets after detachment.
They then coated a layer of PS solution onto the water droplet
array by dip-coating. After the PS solution dried, porous lms
were obtained. Hexagonal, square, and other pore arrays could
be fabricated by varying the substrate wettability, the receding
velocity of the contact line, and the thickness of the cast ethanol
liquid lm (Figure 42eh). The interpore distance (L) and
pore size (D) could be controlled by tuning the humidity of the
air ow during the formation of the water droplet arrays.
Moreover, the pore size could be readily tuned by further water
condensation or evaporation, yielding porous polymer lms
with pore arrays with dierent D/L ratios.
6. CHEMICAL MODIFICATION AND
FUNCTIONALIZATION OF BFA FILMS
Controlling surface properties and chemical functions is one of
the essential goals in the construction of porous materials.
During the BF process, polar groups or segments and NPs will
be selectively enriched on the wall of pores due to the
hydrophiliclipophilic balance and the Pickering eect. This
spontaneous surface heterogeneity benets further chemical
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Figure 42. (ad) Schematic illustration of BFA formation using the
Marangoni ow-induced arrays of water droplets as templates. (eh)
Typical images of porous PS lms with hexagonal (e, f) and square
arrays of pores (g, h) formed by the modied BF process on the SiOx
and Si substrates, respectively. The corresponding relative humidity is
shown at the upper right corner of each image.430 Reprinted from ref
430. Copyright 2009 American Chemical Society.
and physical modication, which may endow the lm with new
functionalization. Accordingly, a variety of chemical and
physical methods have been developed to modify and
functionalize BFAs. Moreover, polymeric matrixes consisting
of linear structures can be cross-linked by postchemical
modication to increase their dimensional stability. This
provides another way to improve the performance of BFAs.
These postmodication methods are summarized in this
section.
6.1. Functionalization of BFA Films
Physical blending and surface chemical modication strategies
have been employed to build functionalized BFA lms. By
casting a mixture of polymer and NPs in solution, the Pickering
eect combined with the BF process can aord additive-
functionalized porous BFA lms. Moreover, the surface
chemical modications are widely performed after the BF
process, and these modications endow the BFA lms with new
functions.
6.1.1. Hybridization with Inorganic Nanomaterials. To
prepare hybrid BFAs, the inorganic nanocomponent is mixed
with a polymer solution, and the blend solution is cast
following a standard BF process. As discussed above, the
nanocomponent may self-assemble at the polymer solution/
water droplet interface and help stabilize the water droplets
(Pickering eect) (Figure 43a).150,432 The Pickering eect in
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Figure 43. (a) Illustration of the formation of hybrid BFA lm. The
particles assemble on the watersolution interface due to the
Pickering eect. (b, c) TEM images of cross section of BFA lm.
The CdSe NPs can be observed as a thin black lm at the polymerair
interface.150 Adapted with permission from ref 150. Copyright 2004
Nature Publishing Group. (d, e) Fluorescence optical microscopic
images of BFA lms of polymer embedded with Ag NPs and CdSe
QDs (ratio 2:1) (d) and with only CdSe QDs (e).437 Reprinted with
permission from ref 437. Copyright 2013 Royal Society of Chemistry.
the BF process leads to the formation of hierarchically
structured NP arrays. Thus far, a great number of nanomateri-
als, such as NPs of Au,433 CdSe,150 Fe2O3,434,435 and SiO2,44,149
CNTs,436 hydrophilic nanoclays,288 surfactant-encapsulated
POMs,146 and amino modied zeolite L crystals,152 have
been reported to be able to form hybrid BFAs.
Russell et al. conrmed the preferential segregation of the
CdSe NPs to the polymer solutionwater interface, where they
formed a 57-nm-thick layer and functionalized the walls of the
holes (Figure 43b,c).150 This process opened a new route to
the fabrication of highly functionalized ordered microarrays of
NPs that are potentially useful in sensors, separation
membranes, or catalytic applications. Cavallini et al. reported
that a 6-fold enhancement of the QD emission was observed
when the QDs were coupled with the near eld from Ag NPs,
which were spatially organized in an ordered BFA (Figure
43d,e).437 Sun et al. proved that silica NPs, PS colloid crystals,
and poly(NIPAm-co-acrylic acid) microgels could be easily
transported to the oil/water interfaces, where they would
stabilize the water droplets and assist the formation of
BFAs.149,438 It was found that an increase in the amount of
particles resulted in an increase in the pore size and a decrease
in the size of the pore intervals. Jiang et al. prepared a
bioinspired BFA lm with PI (80) as a basic structure and
nanoclay as the enhanced layer in the walls. 288 The
introduction of the clay into the lm not only increased the
thermal stability of the materials but also improved the
hardness of the BFA lms 5-fold. In another work, Vohra et
al. prepared electroluminescent polymeric BFA lms with
zeolite nanocrystals of 40 nm diameter that self-organized in
the surface.152 To increase the solubility of zeolite, they
chemically modied their external surface. The dierent
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functionalization of the zeolite surface resulted in dierent
organizations inside the pores of the polymer BFA lm.
The NPs can also be incorporated into BFA lms by in situ
reactions. Xu et al. prepared hemispherical or mushroomlike
TiO2 microparticles from a homogeneous solution of TiCl4/
PS/CHCl3 using the BF method (Figure 44).439 Water droplet
Figure 44. SEM images of ordered composite lms lled with (a)
hemispherical and mushroomlike (b)TiO2 NPs.439 Reprinted from ref
439. Copyright 2011 American Chemical Society.
arrays condensed on the solution surface acted as the
microreactors for the hydrolysis of TiCl4. At the same time,
PS self-organized around the arrays of microreactors to form
an ordered porous matrix. This method is versatileother
polymers can be employed, and other hemispherical or
mushroomlike particles can be obtained by using corresponding
precursors.
6.1.2. Surface Chemical Modication. As mentioned
above, polar segments always localize on the inner surface of
the pores, whereas the hydrophobic segments exist inside and
on the top layer of the lm.319,440 Therefore, it is possible for us
to selectively modify the inner surface of the pores or the top
surface of the BFA lms.441
Juang et al. prepared polyurethane BFA lms from dendritic
side-chain polymers with reactive pendant units.160 Subsequent
chemical modication through reaction with a hydrophobic
poly(oxyalkylene) amine increased the CA from 113 to 134.
Further physical modication through a peeling-o process
gave the lm surface a 3D rod-co-valley structure. This lm
exhibited superhydrophobicity with a CA of 151. Stenzel et al.
sequentially grafted the thermoresponsive monomers N-
isopropylacrylamide (NIPAAm) and N-acryloyl glucosamine
(AGA) onto BFA lms by RAFT polymerization.442 As a result,
the lms displayed switchable hydrophilic/hydrophobic char-
acteristics and were turned into a thermodependent switch for
the selective recognition of biomolecules.
The patterning of biomolecules is an important and
challenging technique. Cortajarena et al. prepared BFA lms
from a mixture of a PS-b-PAA (6) diblock copolymer and a PS
homopolymer.443 They then performed a straightforward
functionalization using ethyl(dimethylaminopropyl) carbodii-
mide as a catalyst to esterify carboxyl groups inside the pores
with dierent polypeptide sequences. Wan et al. prepared BFA
lms with an amphiphilic BCP, PS-b-PHMA (25).143 Three-
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dimensional uorescence results demonstrated that the
hydroxyl groups were primarily inside the pores (Figure 45).
Figure 45. (a) Schematic illustration of site-selective grafting
polymerization from the pore surface of PS-b-PHMA BFA lms and
the subsequent lectin recognition. (b) Three-dimensional confocal
uorescence image of PS-b-PHEMA BFA lm after staining with 5-
aminouorescein.143 Reprinted from ref 143. Copyright 2010
American Chemical Society.
2-(2,3,4,6-Tetra-O-acetyl--D-glucosyloxy)ethyl methacrylate
was selectively grafted in the pores by a surface-initiated
ATRP. Further specic recognition of the carbohydrate
microarrays by lectin (Con A) can lead to an organized
microarray of protein. Another widely used type of reaction for
surface modication is the click reaction.444,445 Kadla et al.
fabricated robust, region selectively modied amphiphilic
cellulose azide BFA lms.29,446 Due to the existence of azide
groups, the BFA lm can be postfunctionalized through the
click reaction as follows: using the Cu(I)-catalyzed alkyne
azide [2 + 3] cycloaddition reaction, biotin is clicked onto the
azide functionalized area in BFA lms without any eect on the
structure of the lm. These results indicated that this system
could serve as a platform for the design and development of
biosensors. The applications of patterned biomolecules will be
further discussed in section 7.
More interestingly, Mun oz-Bonilla et al. reported the
selective functionalization of the top surface of BFA lms
while maintaining the functionality of the pores.107 For this
purpose, they prepared BFA lms with a blend of PS and PS-b-
P5FS (33). The P5FS blocks assembled on the surface of the
lm due to their low surface energy, leading to a hydro-
phobicity of the BFA lms. Thus, the measured water contact
angle of the BFA lms was similar to that predicted by the
CassieBaxter model, indicating that water could not go into
the pores on the BFA lms. Therefore, the top surfaces were
selectively modied with glucose through the click chemistry
reactions between the uorine atoms in the para position of the
pentauorostyrene units along the surface and thiol-protected
glucose (Figure 46a). After deprotecting the hydroxyl groups,
an obvious decrease of the water CA on the surfaces and the
change of elemental composition in the XPS measurements
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demonstrated that the surface modication was successful. This
group also found unprecedented morphologies in BFAs
prepared with an incompatible ternary blend consisting of
high-molecular-weight PS, an amphiphilic BCP of polystyrene-
b-poly[poly(ethylene glycol) methyl ether methacrylate] (PS-b-
P(PEGMA), 138) (Scheme 31), and a uorinated homopol-
ymer, P5FS.138,447 The uorine homopolymer was preferen-
tially situated at the pore edge but formed spherical domains
with narrow polydisperse sizes (Figure 46bd). This
morphology was attributed to the two simultaneously occurring
processes, i.e., the BF process and the phase separation process.
Thiolated glucose molecules could be specically attached to
the P5FS21 domains via a thiolpara uorine click reaction.
6.2. Cross-Linking of BFA Films
Cross-linking is a common method for polymer modication
because of its profound inuence on the mechanical properties
and other characteristics, such as segment mobility, solubility,
and permeability, of polymers. Therefore, cross-linking can
eectively improve the polymer performance in a harsh
environment. Usually, cross-linking reactions can be performed
by thermally, chemically, or photochemically treating the
polymers with cross-linkable reactive groups. As described
below, by carefully choosing suitable reactions, BFA lms can
be eciently cross-linked without damaging their honeycomb
morphology.
6.2.1. Thermal Cross-Linking. A one-step thermal treat-
ment will inevitably cause the linear polymeric microstructure
to completely or partially collapse before the temperature-
sensitive groups totally cross-link. Bunz et al. synthesized azide-
substituted, soluble poly(p-phenyleneethynylene) (PPE, 88)
and prepared its BFA lm.448 Upon heating to 300 C, the
polymer cross-linked, and the thin lm was turned into an
insoluble matrix with isolated pores. However, the pore-lled
structures collapsed on the substrate. To avoid the collapse, a
two-step thermal treatment was adopted by Galeotti and co-
workers.47 First, the pores on the BFA lms were lled with a
liquid PDMS precursor. Then, the PDMS precursor was
solidied at a temperature lower than the Tg of the polymer
matrix. When the temperature was increased further, the
thermal cross-linking of the polymer matrix was initiated. The
solidied PDMS elastomer covering the surface and lling the
pores of the lm worked as a memory mask for maintaining the
microstructure of the BFAs. After cooling and peeling o the
PDMS mask, the polymer lm became insoluble, while the
surface structure was perfectly preserved.
6.2.2. Chemical Cross-Linking. Many simple chemical
reactions can eciently cross-link BFA lms, thus improving
their mechanical strength and chemical stability. Wong et al.
reported the synthesis of silicone-based random branched
copolymers (139, 140) (Scheme 32) containing 3-
(trimethoxysilyl)propyl methacrylate (MPS) and 3-[tris-
(trimethylsiloxy)silyl]propyl methacrylate (TRIS).449 After the
BF process, the presence of alkoxysilane precursors inside BFA
lms enabled the cross-linking of the lm via the solgel
process. Cross-linked BFA lms had enhanced properties,
including higher exibility and better solvent resistance and
thermal stability, which may enable their applications as thermal
sensors or low-cost conformal digital displays when coupled
with thermally sensitive or light-emitting materials inside the
pores.
Karthaus et al. prepared mesoporous BFA lms from
poly(styrene-co-maleic anhydride) (P(St-co-MAH), 141)450
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Figure 46. (a) Schematic illustration of the selective functionalization of the external surface of BFA lms by a mixture of PS and PS-b-P5FS with
glucose moieties and subsequent recognition of Con A.107 Reprinted with permission from ref 107. Copyright 2013 Royal Society of Chemistry. (b)
Illustration of the composition distribution of a BFA lm prepared from a blend of PS, PS-b-P(PEGMA), and P5FS. (c, d) XY (c) and XZ (d) Raman
mappings of the BFA lms prepared from the mixture. Red, PS; blue, P(PEGMA); green, P5FS.138 Adapted from ref 138. Copyright 2013 American
Chemical Society.

Scheme 31. Chemical Structure of PS-b-P(PEGMA) (138)
(Scheme 33). Cross-linking was achieved by immersing the lm
in an ethanol solution of alkyldiamine. The cross-linked
honeycomb structure was stable at up to 350 C, which is
more than 150 C higher than the stability threshold for the
non-cross-linked lms. Inspired by the vulcanization of rubbers,
our group developed a simple technique of cross-linking the
double bonds in SIS by exposing the BFA lm to S2Cl2
vapor.256 The attack of S2Cl2 on the internal vinyl groups of
the polymer leads to the formation of pendant sulfur chloride
groups on the polyimide chains that can act as potential cross-
linking sites (Figure 47a). The reaction of these groups with the
internal vinyl groups on other chains is responsible for the
AN
formation of eective cross-links. After 15 min of vulcanization,
the resulting SIS BFA lms showed high mechanical strength
and good resistance to a variety of organic solvents and strong
acidic and basic solutions (Figure 47be). The cross-linked
lm also remained stable at up to 350 C for 2 h. The versatility
of the methodology was also demonstrated by applying it to
other vinyl group containing polymers.256
6.2.3. Photochemical Cross-Linking. Photochemical
cross-linking is an attractive technique because it is easier to
perform but leaves little or no contamination. Generally,
photochemical cross-linking requires the existence of a
photosensitizer that can generate radicals upon exposure to
visible light, UV light, or high energy radiation. Macroradical
recombination occurs when two radicals meet and form a
covalent bond.
Double-bond-containing polymers are ideal candidates for
photochemical cross-linkage. Karthaus et al. demonstrated that
highly ordered BFA lms can be prepared from a photo-cross-
linkable poly(vinyl cinnamate) (142)/polyion complex (143)
mixture (Scheme 34), and UV cross-linking could be
conducted while retaining the 3D honeycomb structure.451
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Scheme 32. Chemical Structures of Polymers Containing
Cross-Linkable Moieties (139, 140)
Scheme 33. Chemical Structure of P(St-co-MAH) (141)
Figure 47. (a) Cross-linking mechanism of polyisoprene chains. (be)
SEM images of SIS BFA lms thermally treated at 350 C for 2 h (b
d) and immersed in chloroform for 1 min after cross-linking (e).
Vulcanization times: (b) 4 and (ce) 24 h.256 Reprinted with
permission from ref 256. Copyright 2010 Elsevier.
The honeycomb structure was stable against organic solvents
after a threshold cross-linking time of 30 min (Figure 48a,b).
Our group prepared BFA lms with the commercial triblock
copolymer SBS.452 After 1 h of UV irradiation, the SBS lms
became resistant to a wide range of organic solvents and
became thermally stable at up to 350 C. Another benecial
eect of the photochemical process was the formation of polar
groups on the lm surface, which changed the surface
wettability from hydrophobic to hydrophilic. The resulting
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Scheme 34. Chemical Structures of Photochemical Cross-
Linkable Polymers (142144)
Figure 48. SEM images of BFA lms after UV cross-linking and
treatment with heat or organic solvent. (a, b) BFA lms of a poly(vinyl
cinnamate)/polyion complex immersed in chloroform after UV
irradiation for 0 (a) and 30 min (b).451 Reprinted with permission
from ref 451. Copyright 2007 Wiley-VCH. (cf) BFA lms of PS
thermally treated at 250 C (ce) and immersed in chloroform (f)
after UV irradiation. UV irradiation times: (c) 2 and (df) 4 h.45
Reprinted with permission from ref 45. Copyright 2009 Royal Society
of Chemistry.
lms were noncytotoxic and were suitable as cell scaolds.
Recently, Wang et al. prepared and photocured poly(-
caprolactone) triacrylate (144) BFA lms.167 Cell behavior
and gene expression were investigated on these two series of
BFA lms and their at counterparts. Shimomura et al.
prepared bas-relief patterns by selectively UV irradiating BFA
lms containing PB through photomasking.453 After heat
treatment, the non-cross-linked lm was melted, and the
remaining pattern showed a very distinct edge with a 4%
resolution error.
PS and PS-containing BCPs can also be photochemically
cross-linked, although the mechanism is still in dispute.45,222
Under UV exposure, hydrogen atoms at the position of the
PS backbone are extracted, yielding macroradicals along the
polymer chain. A covalent bond then forms when two
macroradicals annihilate by recombination. The cross-linked
PS BFA lms are chemically and thermally stable compared
with their linear cousins (Figure 48cf), which is important for
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Figure 49. Preparation of inorganic honeycomb patterns with BFA templates. (a) SEM image of CNT bundles synthesized from as-prepared PS-b-
PAA/ferrocene BFA lm by chemical vapor deposition (CVD). (inset) Cross-sectional SEM images. (bd) SEM images of silica (b), Fe2O3(c), and
ZnO (d) patterns by pyrolysis of cross-linked PS-b-PAA/precursor composite BFA lms. (b, inset) AFM image of silica pattern. (e) SEM of aligned
CNTs grown with Fe2O3 pattern shown in (c) as a catalyst by a CVD. (inset) Cross-sectional SEM images. (f) ZnO nanorods grown from the ZnO
pattern shown in (d) by a hydrothermal method.223,224 Adapted from ref 223. Copyright 2009 American Chemical Society. Adapted from ref 224.
Copyright 2010 American Chemical Society.

some special applications. For example, the UV cross-linked PS-
b-PAA BFA lm had a char yield of 40% at 450 C, and thus, it
could work as the structure-directing agent to grow CNT and
ZnO nanorod arrays.223 Details of these applications can be
found in section 7. UV irradiation of PS can also induce the
formation of hydrophilic groups and change the surface
properties of the BFA lm. Yabu et al. prepared a
pincushion-patterned lm by removing the top layer of PS
BFA lm.454 Then, they treated the lm with UV and obtained
a hydrophilic surface. Further investigation showed that the
obtained strongly hydrophilic pincushion surface exhibited an
excellent bubble repellency under water.
Additionally, Shimomura et al. prepared BFAs with a mixture
of a photo-cross-linkable epoxy oligomer, a cationic iodide-type
curing agent, and an amphiphilic copolymer.455 By controlling
the UV irradiation time, they successfully regulated the pore
size of the ordered BFAs. After the immersion of the cross-
linked BFA lm in chloroform and ultrasonication, honeycomb
mesh and microdot structures were obtained due to the cross-
linking of the surface.456
7. APPLICATIONS OF BFA FILMS
Great attention has been given to the applications of BFAs. The
characteristic of BFA lms is the hexagonally packed pores on
the lms. Therefore, the applications of BFAs have focused on
how to make use of this unique morphology. Combined with
the dierent functions of various materials, BFA lms have
demonstrated their applications in templating, biology, and
optical and photoelectronic devices, among others. These
applications are categorized and summarized in this section.
7.1. Templates
The BF method is an ecient and cheap method of fabricating
ordered pore arrays. However, the materials that are suitable for
the BF process are limited to soluble polymers and a small
group of other materials. Many other valuable functional
materials cannot be used in the BF process. Therefore, some
researchers have used polymeric BFA lm as the template to
AP
direct the synthesis of other materials with ordered
structures.457460 In general, the BFA lms have been used as
templates, stamps for soft lithography, and masks for etching. In
this section, we focus on the fabrication of inorganic and
polymeric ordered materials with BFA lms as templates. The
patterning of biological molecules will be discussed in section
7.6.
One of the appealing applications of polymer BFA lms is in
directing the growth of inorganic materials, such as ZnO,461
CdS QDs,462 and TiO2.463 To do this, the particles of the
inorganic materials or their precursors should be incorporated
into the BFA lms. After removing the polymer components by
pyrolysis, inorganic BFA lms are obtained. Because the BFA
lms are usually prepared from organic solutions, the particles
or precursors must have good dispersibility or solubility in
these solvents. Many inorganic/organic complexes are desirable
candidates for the precursors. For example, by adding
precursors of 3-amino-propyltrimethoxysilane (APETS), zinc
acetylacetonate (Zn(acct)2), and ferrocene into the solution of
PS-b-PAA, BFAs of SiO2, ZnO, and Fe2O3 were obtained by
subsequently cross-linking and mineralizing the as-prepared
BFA lms (Figure 49).223225 Importantly, the inorganic BFAs
could be further used as catalysts or nuclear sites to direct the
growth of other materials. BFAs of vertically aligned CNTs
(Figure 49a,e) and ZnO nanorods (Figure 49f) were obtained
on the patterned Fe2O3 and ZnO substrates, respectively. Based
on this templating technique, Wan et al. developed a
nonlithographic method to prepare micropatterned ZnO
nanowires (ZnO NWs) with through-pore BFAs as a mask.32
The hexagonally ordered BFA lms with perforated pore
structures were transferred onto Si wafers coated with a ZnO
seed layer. In the subsequent hydrothermal growth, vertically
aligned ZnO NW arrays were formed in the mesh areas. Room-
temperature photoluminescence spectra indicated that the
micropatterned ZnO NWs showed greatly enhanced near-
band-edge emission.
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In some special cases, polymers are themselves precursors of
inorganic materials, and thus, they can produce inorganic
honeycombs without additional reactants.464 For example,
Bunz et al. prepared cyclobutadiene (cyclopentadienyl) cobalt-
containing PPE (145, 146) (Scheme 35) polymers and used
Scheme 35. Chemical Structures of Cobalt-Containing PPE
Polymers (145, 146)
them to prepare BFA lms.465 As a result of the high content of
cross-linkable ethynylene and the rigid molecular chains, the
structures of the BFA lms persisted well during cross-linking
and mineralization at temperatures as high as 600 C. Under
nitrogen, a SiCCo ceramic with low amounts of oxygen was
obtained, whereas in air, all of the carbonaceous matter was
burned o and a SiCoO ceramic of the approximate
composition Co2Si4O11 was formed instead. Yoshie et al.
demonstrated that hypPPV (64) BFA lms exhibited excep-
Figure 50. (a) Schematic diagram of soft lithography to prepare concave and convex arrays of various materials. (b) Digital picture of patterned silk
broin lm showing structural color. (c, d) AFM 3D rendering of silk broin lms patterned with cavity (c) and bump (d) templated from BFA
lms.472 Reprinted with permission from ref 472. Copyright 2012 Royal Society of Chemistry.
AQ
Review
tionally high thermal and chemical stability.193 Furthermore,
simple thermal treatment converted the BFA lm of hypPPV
into a carbonaceous lm without destroying the ordered
structures. PS-b-PDMS BFA lms have also been used to
prepare a SiO2 honeycomb structure through UV cross-linking
and pyrolysis.214 Gong et al. used another silicon-containing
cocopolymer, PDMS-graf t-polyacrylates (PDMS-g-PAs), to
prepare BFA lm.466 After plasma treatment and pyrolysis,
freestanding silicon oxycarbide sheets with ordered through-
pores were obtained.
BFA lms have also been used as templates for in situ
polymerization. For example, Li et al. prepared conducting
polymer polyaniline (PAni) patterns using PC281 or sulfonated
polysulfones (SPSF)467 BFA lms as the template. They rst
soaked the BFA lms in aniline solution for 24 h and then
placed the lm in oxidant solution to perform the polymer-
ization. After polymerization, the PAni/PC or PAni/SPSF
composite lms became electrically conductive while maintain-
ing the honeycomb structure. The BFA structure even survived
after PC or SPSF was removed by soaking in chloroform. Using
a similar method, they also prepared a conductive microlens of
PPy.468 PS-b-PAA BFA lm was also used as a template for the
electrochemical deposition of PAni.168
The highly ordered structure of BFAs has also been
transferred to other materials through soft lithogra-
phy.268,469471 As shown in Figure 50a, concave and convex
arrays can be obtained by one or more steps of lithography,
respectively. One representative example of this templating
application was reported by Galeotti et al., who prepared silk
broin lms with structure color, as shown in Figure 50b.472
Concave or convex microlens arrays, as well as packed
micrometric bump arrays, were molded from PS BFA lms
(Figure 50c,d). This strategy is attractive for the development
of new biocompatible photonic devices. They also found that
when a PDMS replica was peeled away from the PS BFA lm, a
thin layer of PS residues covered the surface of the PDMS
replica.473 The authors released the PS residue onto a Si
substrate by placing the PDMS stamp on the Si substrate and
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Figure 51. (a) Schematic diagram of the preparation of the SERS substrate with pincushion structure. (b) Raman scattering spectra of the R6G
measured on the silver at and pincushion lms, respectively. Inset shows the chemical structure of R6G. (c) SEM image of the silver pincushion
lms. Inset shows close-up image of the top of a spike. Scale bar: 500 nm.480 Adapted with permission from ref 480. Copyright 2010 Royal Society of
Chemistry.
heating it over the Tg of PS. As a result, a hydrophobic PS
pattern was created on the hydrophilic Si surface. Finally, the
patterned Si surfaces were treated with the water solution of
CdTe QDs; the nanocrystals aggregated only on the hydro-
philic areas such that an array of hexagonally ordered
uorescent spots was produced.
Another application of BFA lms is in inductively coupled
plasma reactive ion etching (ICP-RIE), wet etching, and
electrodeposition, where BFA lms are employed as masks to
transfer the honeycomb pattern to the substrates.474,475 For
example, Hirai peeled o the top layer of a BFA lm and used it
as a mask for lithography.57,476 The nanospike arrays were
transferred to the silicon with various crystal facets, and the
obtained surfaces showed antireective properties and super-
hydrophobicity. A metal mask with a honeycomb pattern could
also be prepared by sputter-coating a BFA lm. When the
metals were deposited at vertical incidence, an ordered array of
metal spots could be obtained by peeling o the top layer of the
BFA lms. After the ICP-RIE process, an array of silicon
cylinders was obtained, which could be used as a photonic
crystal lter.477 Our group deposited metal at a title incidence
on the BFA lm.40 After removal of the polymer with organic
solvent, a metal layer with a honeycomb pattern formed on the
substrate, and the pattern could be transferred onto the
substrate surface by etching. Using this method, various
substrates were patterned, including silicon, glass, and Te-
doped silicon.
7.2. Surface Enhanced Raman Scattering Substrates
Periodically arranged nano- and microstructures of noble
metals have proved to be good candidates as substrates for
SERS, which is based on enhanced electromagnetic elds due
to localized surface plasmon resonance.478 The nanostructures,
such as sharp edges and NPs, are the factors that enhance
SERS. Polymer pincushion lms with hexagonally arranged
spike structures can be prepared by simply peeling o the top
layer of the BFA lms with adhesive tape. Metals can be
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deposited onto the pincushion lm by electroless plating or an
evaporation technique (Figure 51).184,479 Accordingly, Shimo-
mura et al. deposited silver on pincushion lms and used these
lms as SERS substrates. Raman spectra demonstrated that the
obtained SERS substrate could detect rhodamine 6G (R6G) at
concentrations as low as 0.5 nM (Figure 51b).480 In addition,
the silver pincushion lms can be prepared on a wide surface
area, and they are exible and freestanding after removal from
the glass substrate.
Wan et al. developed another approach to prepare highly
sensitive SERS substrates with BFA lms decorated by Ag
NPs.233 The silver NPs, with diameters from 18 to 30 nm, were
generated in situ by reducing Ag+ adsorbed on the PDMAEMA
BFA lm. Substrates prepared under optimal conditions had
enhancement factors as high as 106108, depending on the
ratio of the number of analytes to Ag NPs. Hao et al. directly
prepared substrates for SERS using blends of polymers and Au
NPs modied by mercaptan.154 Because of the Pickering eect,
the Au NPs were enriched on the pore walls. They investigated
the relationship between the morphology of the Au BFA lms
and their performance as the substrates for SERS and found
that for R6G, the more regular the BFA lms, the stronger the
SERS signals. They claimed that the more regular BFA lms
had large surface areas that allowed them to adsorb more
analytes from the surrounding solution.
7.3. Separation
Size-based separation is an important application of porous
polymeric membranes. Microsieves are advanced ltration
membranes characterized by uniform pore size, high pore
density, and a thickness smaller than the pore diameter.
Microsieves provide high selectivity, high ux, and the ecient
removal of lter cake by back ushing. To be used as
microsieves, BFA lms should have perforated pores of uniform
size with a hydrophilic surface and high mechanical and thermal
stability. Such perforated BFA lms were prepared with
modied BF methods (using ice substrate, liquid substrate,
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Figure 52. Mechanical properties and separation performance of cross-linked SIS BFA lms with perforated pores. (a) Typical stressstrain curves
of the SIS membranes with dierent vulcanization times, commercial lter papers, and PTFE lter membranes. (b) Graphical comparison showing
the resistance of the SIS membrane to the organic solvents, acid, and base. (cj) Results of separation experiments. (cf) Size distribution of the
feeding particles composed of 500 nm and 3 m PS microspheres (c) and the particles in ltrate obtained by ltering the feeding dispersion solution
in water at 25 (d) and 90 C (e) and in THF (f) through the SIS microsieve. (gj) Corresponding SEM images of the particles.255 Adapted from ref
255. Copyright 2012 American Chemical Society.

dip-coating, or rapidly removing excess solution), as discussed
in section 5.8. The performance of these BFA lms is
summarized in this section.
Cong et al. prepared perforated brominated PPO (82) BFA
lms with controllable pore sizes ranging from 4.5 to 1.0 m by
adjusting the solution concentration.411 A maximum water ux
of 25 m3 h1 m2 was achieved under a feed pressure of 0.13
MPa. With a similar method, Gao et al. produced microsieve
lms from a miktoarm star copolymer containing PS and PtBA
components.171 Partial hydrolysis of the PtBA arm species in
the BFA lm converted the surface wettability from hydro-
phobic to hydrophilic, facilitating the size sorting of colloidal
particles in aqueous dispersion. The microsieve lm, with a
pore size of 1.4 m, could eectively separate PS microspheres
of 650 nm from those of 2 m. Wan et al. prepared a PS-b-
PDMAEMA (24) BFA lm with perforated pores on a soft
substrate with a pore size of 3 m.409 The lm showed a high-
resolution separation performance of PS particles with sizes of
2.0 and 5.0 m. They also introduced an elastic copolymer
(SIS, 47) into the membrane to enhance their tenacity and the
interfacial strength between the membrane and the support.481
Unfortunately, the non-cross-linked polymer membrane is not
freestanding, and thus, the lter membrane must be supported
by a stainless steel woven wire mesh.
Recently, our group demonstrated that vulcanized SIS BFA
lms with perforated pores showed good mechanical properties
and excellent chemical and thermal stability.255 Due to the
cross-linked chemical structure, this type of microsieve was
freestanding and resistant to a variety of polar organic solvents
and acidic, basic, and hot water (Figure 52a,b). The pores on
SIS BFA lms were highly ordered and tunable, with sizes
ranging from 1 to 7 m. The vulcanized SIS microsieve
successfully separated microparticles not only in water at room
temperature but also in hot water and THF (Figure 52ch).
These characteristics make the vulcanized SIS membrane an
AS
ideal microsieve with potential applications in industry.
Mansouri et al. also fabricated robust microsieves with the BF
method by using engineering PSF plastics (82).68 In their work,
ltration membranes with isoporous structures on the surface
of a nylon mesh were prepared by a combination of dip-coating
and the BF approach. Although the ux was lower than that of
commercial membranes, their separation eect was comparable.
7.4. Optical and Optoelectronic Devices
Periodic microstructures are frequently used in optical and
optoelectronic devices, including microlens arrays (MLAs),
micropatterned light emitting diodes (LEDs), antireective
(AR) coatings, solar cells, photonic crystals, and optical sensors,
due to their unique interaction with light. The size of the
periodic microstructures in BFAs falls within the range of
hundreds of nanometers to tens of micrometers, matching the
requirements of optical and optoelectronic devices.482,483
Therefore, the BF process provides a simple and cost-eective
route to prepare ordered microstructures with large areas for
optical and optoelectronic devices.
MLA, an important component for devices used in optical
telecommunication, displays, and solid-state lighting, has been
prepared by molding the pores in BFAs. Spherical and
hemispherical MLAs (Figure 53a,b) were obtained by molding
the as-prepared BFA lms and BFA lms with the top layer
peeled o, respectively.484 Anamorphic MLAs have also been
prepared by molding the anamorphic BFA lms, which were
fabricated by mechanically stretching BFA lms at a temper-
ature above their Tg (Figure 53c).484,485 Considering the
demolding process, PDMS is the most suitable material for
preparing MLAs because it has low surface energy and is easily
peeled away from the mold after solidication. To prepare
MLAs with other materials, Chari et al. created a low-surface-
energy nonstick surface on BFA lm via a surface
reconstruction process after heating the BFA based on a
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Figure 53. (ac) SEM images of spherical (a), hemispherical (b), and
anamorphic MLA (c).484,485 Adapted from ref 484. Copyright 2005
American Chemical Society. Adapted with permisssion from ref 485.
Copyright 2008 AIP Publishing. (d) Setup for measuring optical
diusion. (e, f) Optical diusion through plane glass substrate, MLAs
with diameters of 6 and 3 m, respectively.486 Reprinted with
permission from ref 486. Copyright 2008 the Optical Society.
PDMS-containing copolymer in dry air.485 During this process,
the low-surface-energy PDMS segments migrated to the surface
of the BFA lm, yielding a nonstick surface. This nonstick
template enables the fabrication of MLA using a variety of
polymer precursor materials. For example, polyurethane MLA,
which showed a relatively high refractive index (1.54) and E
(138 MPa), was prepared with the above method.
The main applications of MLAs are in light modulation,
which is aected by the shape and size of the microlens in the
MLAs. For example, the projection images from hemispherical
MLAs are sharper than those from spherical MLAs.484
Anamorphic MLAs eectively redistribute the luminance
angularly when illuminated by a collimated beam.485 Another
important application of MLAs is as light diuser lms to
spread and homogenize nonuniform illumination. As shown in
Figure 53dg, the obtained PDMS MLAs molded from BFA
lm distributed the point light source eectively. The haze
distribution propagated through MLAs with a lens diameter of
3 m was more uniform than that with a diameter of 6 m.486
Further studies showed that 3D BFA lms could be directly
used as a diuser of microcavity organic light emitting diodes
(OLEDs), eectively reducing the viewing angle dependency of
OLEDs.487 When PDMS MLAs were patched outside the
OLED, it was found that the external quantum eciency
(EQE) of a green OLED was enhanced by 32%, and the
enhancement was found widely, at viewing angles between 30
Figure 54. (a) Schematic illustration of the microcontact printing method for the fabrication of patterned OLEDs. (bd) Electroluminescence and
(eg) photoluminescence of the red, green, and blue OLEDs fabricated by microcontact printing. (h) SEM image of the aluminum electrode
surface.490 Reprinted with permission from ref 490. Copyright 2005 Elsevier.
Review
and 60.488 Similarly, in another work, BFA lms directly
enhanced the eciency of a blue LED by 17.7%.489
Microstructured LED arrays, including dot arrays and
network arrays, have been prepared based on BFA lms.490
For example, a dot-array OLED was prepared by a micro-
contact printing method using an MLA-like PDMS stamp
molded from BFA lm and an electroluminescent polymer
solution as ink (Figure 54). Red, green, and blue OLEDs were
all obtained simply by changing the polymer inks. The dot array
had a diameter as small as 1 m, indicating that a high display
resolution of 640 000 pixels mm2 could be achieved. To avoid
the degradation of emissive performance caused by direct
contact between the active polymer and the stamp, Bradley et
al. developed a new method. They added an insulating layer of
polyimide between the active layer and the metal layer.491 By
patterning the PI layer with a PDMS stamp, a dot-array OLED
was also obtained, which had current and power eciencies
twice as high as those for nonpatterned OLEDs.
Another important application of surface microstructure
control is in AR coating, which is used to maximize the
transmission of light through an optical surface. The principle
of AR is based on the destructive interference between the
reected light from the aircoating and coatingsubstrate
interfaces, which can be produced by the porous structure in
the coating due to the decreased refractive index. Therefore,
BFA lms are potential candidates for AR coating. Kim et al.
reported that a CAB BFA lm with two-layer pores
demonstrated broad-band antireection at near-infrared wave-
lengths.492 The reectivity of glass was reduced from over 4%
to less than 1% by the AR coating (Figure 55a,b). Generally
speaking, it is dicult for conventional BFA lm to be used as
an AR coating for visible and UV light because the pore size is
much larger than the wavelength of visible and UV light.
However, Shimomura et al. prepared a BFA lm with 300 nm
pores by reducing the thickness of the cast polymer solution to
less than 100 m.493 The as-prepared BFA lm was
transparent; the 300 nm pores did not scatter visible light.
Over a wide range of UVvis spectroscopy, the transmittance
of the lm with 300 nm pores was higher than 80%, whereas
that of the lm with 2 m pores was only 50%, demonstrating
the high antireective eect of small pores on visible light.
Recently, Trespidi et al. constructed a nanostructured PDMS
AR coating molded from a BFA with pore sizes less than 300
nm (Figure 55c,d).494 The AR coating increased the glass
transmission to more than 2% at normal incidence in the
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Figure 55. (a) SEM images of a CAB lm with two layers of BFA.
Inset shows the cross-sectional image. (b) Reectance of glass coated
with CAB lm and bare glass. The symbols and solid line represent the
reectance measured and calculated from the characteristic matrix
theory, respectively.492 Reprinted from ref 492. Copyright 2005
American Chemical Society. (c) SEM tilted view of the PDMS AR
coating. (d) Single surface reection curves taken at normal incidence
for bare glass, typical MgF2 AR coating, and patterned PDMS-coated
glass.494 Reprinted from ref 494. Copyright 2014 American Chemical
Society.
visible/near-IR spectrum, which corresponds to 50% reduced
reection. Furthermore, eective improvement was observed at
a wide range of incident angles from 90 to 50. The
performance of this PDMS AR coating is better than the
commercial high-performance broad-band AR coating of MgF2.
Because BFA lms can reduce reectivity, they are expected
to enhance the light harvest and improve the performance of
solar cells and photocatalysts. For example, the BF method was
used to prepare a highly ordered porous lm of the light-
emitting rodcoil BCP PDTG (41).249 When irradiated by
white light, the BFA lms showed a photocurrent 3 times
higher than that of the smooth lm. Chen et al. prepared a
porous photovoltaic electrode of rGO/DODA/TiO2 NP
(rGO/DODA/P25) by the BF method.369 The photoactive
TiO2 NPs were enriched on the walls of the pores because of
the Pickering eect. The introduced porous structure and NPs
reduced the reection of the lm to as low as approximately 4%
in the UV range and 10% in the visible range. Because of the
low reection and hybrid structure of the TiO2 NPs strongly
anchored on rGO, the BFA lm showed a photocurrent 2 times
that of smooth TiO2 lm under the same conditions.
In addition, BFA lms have also shown potential applications
in other optical devices, such as photonic crystals and novel
optical sensors. Bormashenko et al. prepared 2D tunable
photonic crystals by coating a PC BFA lm on a PVDF lm.282
Investigation of the transmittance spectra demonstrated that
the photonic band gap of the PC/PVDF lm was located at a
wavelength of 0.95 m. Combining the excellent thermal and
mechanical properties of PC and PVDF, the obtained structures
may have various optical engineering applications. Further-
more, Cusano et al. constructed an optical sensor with high
sensitivity to the surrounding environment by coating metallo-
dielectric BFA lms on the tip of optical ber.495 The
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Review
wavelength of the reection minimum shifted linearly with
the surrounding refractive index, demonstrating the potential of
BFA lms as optical sensors.
7.5. Chemical Power Source
The lithium ion battery is one of the most important energy
storage devices. The porous structure of the BFA lm anode
can promote the mass transfer in the electrolyte and provide
sucient space to release the volume expansion in the charge/
discharge process.496,497 For example, Tu et al. prepared a Si/
honeycomb reduced graphene oxide (Si/H-rGO) hybrid lm
with the BF method.498 Si NPs were uniformly dispersed in the
pores of the BFA lms. rGO not only improved the electric
conductivity of the hybrid BFA lm but also avoided the
aggregation of the Si NPs during cycling (Figure 56a,b).
Figure 56. (a) SEM and (b) TEM images of Si/H-rGO composite
BFA lm. (c) Rate capability of Si/H-rGO composite lm and pure
silicon at various current densities ranging from 50 to 1000 mA g1.498
Reprinted with permission from ref 498. Copyright 2014 Royal Society
of Chemistry.
Meanwhile, the BFA structure oered abundant pathways for
ecient Li+ diusion and balanced the volume variation of Si
during the Li alloying and dealloying processes. Therefore, the
Si/H-rGO lm had both a high reversible capacity (1118 mA h
g1 at 50 mA g1 for up to 50 cycles) and good high-rate
capability (Figure 56c). Lee et al. prepared an Fe-doped MnxOy
membrane with hierarchically connected macropores and
mesopores using a BFA lm of amine-functionalized
bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide)
(BPPO) as the sacricial template.499 When used as the
anode of a lithium ion battery, Fe-doped MnxOy showed large
reversibility (620 mA h g1 at 200 mA g1 for up to 100 cycles),
a good rate (up to 1600 mA g1), and an outstanding cycle life
even at very high current density (900 cycles at 1500 mA g1).
In addition to above electrode materials, BFA lms have also
shown potential application as polymer electrolyte membranes
for lithium ion batteries. For example, Wang et al. prepared
PVDFHFP BFA lms with interconnected multisized pores as
shown in Figure 57a.500 The BFA lms had a porosity of 78%,
which led to a high electrolyte uptake of 86.2%. The pore size
and porosity decreased from the front side to the back side of
the lm, which prevented lithium dendrite growth and short
circuit when applied in lithium ion batteries. Moreover, the
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cell culture, biomedical devices, and tissue engineering, among

others. BFA lms are promising substrates for patterning
biomolecules because of the ordered packed pores on the
surface and the dierences in surface chemical composition
inside and outside the pores. Water-soluble blocks and polar
groups of amphiphilic polymers are enriched on the pore wall
and provide the chemical sites for the modication of
biomolecules.503 For example, Zhang et al. used a blend of
PS and amino-terminated PS to prepare BFA lms with pores
decorated with amino groups. Proteins were successfully
conjugated to the amino-terminated pore surface through the
cross-linking of glutaraldehyde (Figure 58).270 Stenzel and

Figure 57. (a) SEM images of PVDFHFP BFA lms. The inset is the
back side. The front side is ordered porous structure, while the back
side has much less density of pores with smaller size. (b) Combustion
test of the BFA lm after set on re, showing its reproof property. (c,
d) Electrochemical performances of lithium ion cells with LiFePO4 as
cathode materials. (c) Cycling performances. The cuto voltages are 2
and 4.2 V. The current density is 0.2 C (1 C = 170 mA g1). (d) Rate
behavior. Reprinted with permission from ref 500. Copyright 2014
Nature Publishing Group.

BFA lms were also thermally stable up to 350 C and

noncombustible in re (reproof), as shown in Figure 57b. In Figure 58. Fluorescence images of PS BFA lm after uorescein
order to make better polymer electrolyte membranes, the isothiocyanate conjugated bovine serum albumin (FITC-BSA) is
authors combined two BFA lms to one membrane by putting attached to the amino-terminated surfaces. (a) Two-dimensional top
the front sides together with the back sides exposed to the view. (b) Three-dimensional confocal image. (c) Confocal slice images
outside. The combined membranes exhibited a high ionic at dierent z positions (s1, s2).270 Reprinted with permission from ref
conductivity of 1.03 mS cm1 at room temperature, which was 270. Copyright 2007 Wiley-VCH.
much higher than that of commercial polymer membranes of
Celgard 2400. When the combined lms were applied in
Rodriguez-Herna ndez also developed several BFA lm
lithium ion batteries with LiFePO4 as cathode materials, the
substrates for protein patterning.443,504 They used PS-b-PAA
voltage dierence between charge and discharge curves was
to prepare BFA lms. The high hydrophilicity inside the pores
smaller than 0.1 V, and the reversible capacity was much higher
of the BFA lms ensured the penetration of all reactants into
than that of a battery with Celgard 2400 as electrolyte, as
the pores. Consequently, biotin molecules were selectively
shown in Figure 57c. In addition, the higher capacity at lower
bonded on the pore wall. An organized array of proteins was
current density could be repeated after several cycles at higher
obtained based on the molecular recognition between biotin
current density as shown in Figure 57d, illustrating that the
and streptavidin. They also prepared copolymers containing -
PVDFHFP polymer electrolyte membranes could support
galactose moieties to construct BFA lms with bioactivity. Most
outstanding rate performance.
of the peanut agglutinin protein was conjugated to the
Porous structures in electrodes are also very important for
glycopolymer inside the pore, indicating the excellent selectivity
the performance of solid oxide fuel cells (SOFCs) because they
of the template.124 Furthermore, glycopolymer BFA lms could
can provide more electrochemical sites and supply a trans-
be used to recognize Con A,125,143,241 and their bioactivity can
portation path for oxygen and the generated electrons.
be tuned between on and o states based on temperature
Accordingly, Sun et al. dispersed La0.8Sr0.2MnO3/8YSZ (8
due to the thermoresponsive property of PNIPAm.505
mol % Y2O3-doped ZrO2) (LSM/YSZ) and
Another strategy to pattern proteins is to ll the pores of
La0.6Sr0.4Co0.2Fe0.8O3Gd0.2Ce0.8O2 (LSCFGDC) in an
BFA lms with microspheres decorated with biomolecules or
organic solution of SIS and prepared porous BFA lms on the
bioactive molecules.506508 PS microbeads with comparable
YSZ substrate with those solutions by a conventional BF
size have been successfully trapped within the pores of BFA
process.501,502 Then, the porous composite BFA lms were
lms (Figure 59).136 Because the microbeads can be modied
used as cathodes of SOFCs. Electrochemical impedance
with various biomolecules, bead-based protein bioassays can be
spectroscopy (EIS) measurement showed that the porous
constructed following this strategy. Wan et al. also assembled
BFA lms eectively reduced the polarization resistance
microspheres decorated with glucose in the pores of BFA lms.
because of the improved diusion of oxygen and the easy
The functional arrays produced were used to recognize Con
transportation of electrons.
A.509
7.6. Micropatterning of Biological Molecules The other way to construct biomolecule patterns is to
Micropatterns of proteins have attracted increasing interest directly use these molecules to prepare BFA lms. To do so,
because of their potential application in biosensors, biocatalysis, water-soluble biomolecules must be decorated to increase their
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Figure 59. (a, b) Optical (a) and uorescence (b) images showing the
patterning of uorescent PS microbeads on BFA lm. (c) Line-prole
graph with peaks corresponding to the microbeads indicated by the
white line in (b). (d) Fluorescence image of patterned PS microbeads
immobilized with FITC-BSA on BFA lm.136 Reprinted with
permission from ref 136. Copyright 2006 Wiley-VCH.
solubility in organic solvents. For example, Wu et al. developed
a strategy for preparing DNA micropatterns using DNA/
cationic surfactant (DTDA) complexes as a raw material
(Figure 60a).510 The electrostatic interaction between the DNA
Figure 60. (a) SEM image of DNADTDA complex BFA lm (tilted
60).510 Reprinted from ref 510. Copyright 2009 American Chemical
Society. (bd) Confocal images of POM-patterned PMMA lm
before (b) and after encountering the immersion in hemoglobin-Cy3
(c) and FITC-BSA (d) aqueous solutions.69 Reprinted with
permission from ref 69. Copyright 2013 Elsevier.
and the cationic surfactant allowed them to modify the DNA
with noncovalent interactions and to render it soluble in
chloroform. Ordered BFA lms were successfully prepared with
this chloroform solution. Galeotti et al. also directly patterned
biological molecules by using microprinting methods with
patterned PDMS as a stamp, which was a replica of BFA
lms.511 Microemulsion BFAs are another way to pattern
water-soluble biomolecules.512 Wu et al. prepared an inverse
microemulsion with an aqueous solution of bovine serum
albumin (BAS) and polymer organic solution. The micro-
emulsion was then cast onto a substrate and allowed to dry,
yielding BFA lms. BAS was found anchored on the pores of
the BFA lms. The obtained BAS patterns could be locally used
to detect other proteins through specic recognition.71 Using a
similar method, they also constructed the POM pattern, which
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was subsequently used to selectively adsorb proteins through
their electrostatic interactions with POMs, thus producing
protein patterns (Figure 60bd).69
7.7. Cell Culture and Inhibition
Cell behaviors, including cellular adhesion, spreading, pro-
liferation, dierentiation, and gene expression, are regulated by
the interactions between cells and their microenvironments.
Therefore, the chemical, mechanical, and topological properties
of scaold surfaces play important roles in the control of cell
behaviors. BFA lms have surface chemical heterogeneity and
adjustable surface topology, and thus, both the as-prepared and
the chemically modied BFA lms have been demonstrated to
be promising scaolds for cell culture and the investigation of
cell behaviors.513515
The behaviors of various types of cells have been investigated
systematically on BFA lms of amphiphilic and biodegradable
polymers, including PLA (100), PCL (101), PLGA (102), and
others.319,516,517 Compared with at lms, BFA lms with an
appropriate pore size can promote the adhesion and
proliferation of most normal cells, including endothelial
cells, 518,519 broblasts, 520 chondrocytes, 521,522 hepato-
cytes,183,523 neural stem cells (NSCs),524 preosteoblastic
cells,525,526 and human mesenchymal stem cells.527 BFA lms
have also demonstrated capacities to control the morphology
and dierentiation of cultured cells, which was crucial for tissue
engineering. These cells include hepatocytes,528 NSCs,529
breast epithelial cells,530 osteoblasts,167,328 stem cells,527
endothelial cells, 531 mesenteric-stromal vascular cells
(mSVCs),532 and mast cells.533 For example, on a at lm,
hepatocytes had a typical monolayer spreading morphology
after culturing for 72 h (Figure 61a).528 However, on BFA lms
Figure 61. (a, b) CLSM images of actin localization in adhered
hepatocytes after 72 h of culture on (a) at lm and (b) BFA lm.528
Reprinted with permission from ref 528. Copyright 2005 Elsevier. (c,
d) SEM images of neuron cell morphologies after culturing for 5 days
on at lm (c) and BFA lm with pore sizes of 3 m (d).524 Reprinted
with permission from ref 524. Copyright 2004 The Society of Polymer
Science.
with a pore size of 5 m, the cell spreading was inhibited, and
the hepatocytes showed a spherical morphology (Figure 61b).
The size of the spheroids was approximately 100 m after 24 h.
Importantly, the urea level of spherical hepatocytes was higher
than that of the monolayer hepatocytes. Thus, the hepatocytes
on the BFA lms formed as tissuelike structures and displayed
appropriate liver-specic functions. Further investigation
showed that the dierentiation of NSCs could be controlled
by the pore size of BFA lms.529 The NSC dierentiation was
suppressed by the BFA lm with pore sizes of 3 m, specically
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due to the adhesion arrangement of the NSCs (Figure 61c,d).
Recently, it was reported that BFA lm could promote the
epithelial dierentiation and growth of breast epithelial cells
(MCF-7) because of the increased expression of mammary
dierentiation genes (GATA3, EMA, and INTEGB4) and the
repressed expression of a mesenchymal gene (CALLA) (Figure
62).530 In addition, it was found that the pattern geometry
greatly inuenced the morphology of cells, because the pore
walls guided the spreading of the cells.315,534
Figure 62. Morphology of MCF-7 cells cultured on dierent scaolds.
(a, c) On a PLGA plate. (b, d) On dip-coated PLGA BFA lm. (a, b)
Optical images. (c, d) SEM images. (e) Representative plot of
semiquantitative RT-PCR expression data for GATA3, EMA,
INTEGB4, B2MG, Notch1, and CALLA. 530 Reprinted with
permission from ref 530. Copyright 2013 Wiley-VCH.
The surface chemical and mechanical properties of BFA
lms, such as hydrophobicity, surface charge, and hardness, can
also have a tremendous inuence on cell behaviors.33,452,535
Generally, a charged, hydrophilic, hard surface is desirable for
cell culture. Stenzel et al. prepared a soluble PPy composite
using an amphiphilic BCP of PS-b-PAA as a dopant and
stabilizer (18).226 The BFA lms based on this PPy composite
were noncytotoxic and were suitable as scaolds for tissue
engineering. Initial broblast cell culture studies on these
scaolds demonstrated a dependency of cell attachment on the
pore size of the scaolds.
BFA lms based on small molecules and inorganic materials
were also employed as substrates for the investigation of cell
behavior. Li et al. prepared FF (124) BFA lms and cultured
human embryonic skin broblasts (ESFs) on them.374 ESFs
adhered, spread, and grew better on FF BFA scaolds than on
FF organogels due to the honeycomb structure and surface
roughness. They also prepared TiO2 BFA lms consisting of
anatase nanocrystals, starting from a titanium n-butoxide
(TBT) solution.536 The cell adhesive and proliferative
capacities on TiO2 BFA lms with dierent pore sizes were
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evaluated through NIH 3T3 broblast cell-culture experiments.
Compared with the spherical morphology on titanium foil, a
at morphology of cells was found on the TiO2 BFA lms with
pore sizes of 4.6 m, showing enhanced cell adhesion and
spreading. The improved adhesion, spreading, and proliferation
of the cells demonstrated excellent biocompatibility for the
TiO2 BFA lms.
The inhibition of cancer cells and bacteria by BFA lms has
been investigated by some research groups.514,537,538 Tang et al.
prepared BFA lms with polymers (147) containing TPE units
(Scheme 36), which had an AIE property.539 They found that
Scheme 36. Chemical Structure of Polymer Containing TPE
Unit (147)
the BFA lm was not benecial for the growth of cancer cells
because of a relatively large hydrophobic property and the
presence of air in the pores (Figure 63). Shiratori et al.
Figure 63. (ac) Fluorescence and (df) SEM images of HeLa cells
grown on a glass surface (a, d), smooth lm (b, e), and BFA lm (c,
f).539 Reprinted from ref 539. Copyright 2013 American Chemical
Society.
demonstrated that PS BFA lms with pore sizes of 511 m
showed eective inhibition to bacterial adhesion, growth, and
biolm formation. According to bacterial proliferation tests, the
area covered by bacteria on the BFA lm was only 0.59% that
of the area covered on at lm.540 In another work, dodecyloxy-
azo-zinc phthalocyanine (daZnPc, 130) was chosen to fabricate
a nanoscale BFA lm.380 This novel BFA lm could generate
excited-state singlet oxygen (1O2) under irradiation, which
caused irreversible oxidative lethal damage to bacterial cells.
Therefore, the daZnPc BFA lms exhibited a robust photo-
dependent antibacterial eect against E. coli. According to the
same mechanism, BFA lms containing Mn(III) meso-tetra(4-
sulfonatophenyl) porphine chloride (MnTPPS) also showed an
improved antibacterial eect compared to the at lm.379 BFA
lms made of cellulose with a quaternary ammonium (QA)
structure also exhibited eective antibacterial activity against E.
coli.327 Recently, Rodriguez-Hernandez also found that BFA
lms of polyimide-g-PEO/polyimide could eectively prevent
the adhesive Staphylococcus aureus, which may attribute to
hydrophilicity of pore walls.440 Further investigation showed
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that the BFA lms demonstrated antifouling properties in
addition to antibacterial activity. Antifouling BFA lms, which
had a multigradient porous surface, were also reported by
Rodriguez-Hernandez et al. in their recent work.541 In addition,
BFA lms could potentially be used as a physical shield to
prevent intraperitoneal adhesion after abdominal surgery.542
7.8. Sensors
BFA lms have been used as biosensors with high sensitivity.
For example, Wang et al. fabricated a biosensor of nano-
electrode ensembles (NEEs) by constructing a PS-b-PAA BFA
lm on the surface of a glass carbon electrode.543 Cyclic
voltammograms demonstrated that the NEEs drastically
suppressed the response of ascorbic acid (AA) and resolved
the overlapping voltammetric response of uric acid (UA) and
AA into two well-dened peaks with a large anodic peak
dierence (Epa) of approximately 310 mV (Figure 64). Thus,
Figure 64. (a, b) Cyclic voltammograms of 1 mM AA (black line) and
0.5 mM UA (red line) on a glassy carbon electrode (a) and on NEEs
(b) in 0.10 M PBS (pH 6.86). Scan rate: 50 mV s1. (c) Plot of the
anodic peak current of cyclic voltammograms against the concen-
tration of UA. (d, e) Top view (d) and cross-section view (e) of PS-b-
PAA BFA lm on the electrode.543 Reprinted with permission from ref
543. Copyright 2006 Elsevier.
the precise detection of UA could be achieved in the presence
of AA. The peak current obtained from dierential pulse
voltammetry (DPV) increased linearly with the UA concen-
tration within the range 0.2550 M, and the detection limit
was as low as 0.04 M (S/N = 3). Furthermore, the NEEs
showed excellent sensitivity and selectivity in the detection of
UA in serum and urine samples. In another example, Wan et al.
constructed a glucose sensor with a BFA lm based on
polymers containing phenylboronic acid (PBA).144 It was
demonstrated that the PBA groups aggregated on the pore
walls of BFA because of their hydrophilicity, which could
benet the contact between the PBA and the glucose. These
PBA-functionalized BFA lms had high sensitivity toward
glucose, as shown by the QCM results. Furtherly, Wu et al.
loaded insulin into PBA-modied BF pores, and based on the
sensing property of PBA to glucose, glucose-responsive release
of insulin was realized.544
Besides the above biosensors, BFA lms have also shown
potential applications in other kinds of sensors. For example,
Sun et al. prepared BFA lms with a mixture of PS and
uorophore pyrene.545 The uorescence of BFA lms could be
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Review
rapidly and selectively quenched by a nitroaromatic. Therefore,
the uorescent BFA lms can be applied as explosive sensors.
In another work, porphyrinated polyimides (148) (Scheme 37)
Scheme 37. Chemical Structure of Porphyrinated Polyimide
(148)
were used to prepare to BFA lms, which had a similar
uorescence emission property with porphyrin.546 Especially,
the porphyrinated BFA lms showed remarkable uorescence
quenching behavior toward HCl gas because HCl protonated
the porphyrin moieties and changed their conformation from
planar to saddle structure, demonstrating high sensitivity to
HCl. Also, the quenched uorescence emission property could
be recovered by ammonia gas, showing excellent reusability of
the BFA lms. In addition, the BFA lms had a high thermal
stability and kept high sensitivity to HCl gas even at a
temperature as high as 300 C.
7.9. Miscellaneous Applications
In addition to the aforementioned applications, BFA lms have
also been used in catalysis, stimuli-response devices, water
collection, and other applications. Some representative
applications are reviewed below.
Catalysts are usually loaded on a porous matrix to enhance
their activity.280 Accordingly, Save et al. introduced a Rose
Bengal (RB) photosensitizer into BFA lm by using a special
copolymer of P(S-stat-VBC)-g-RB (44).252 Due to the
hydrophilicity of RB molecules, they were enriched on the
pore walls of the BFA lm, which enhanced their contact with
reactive molecules. Thus, the photoactivity of RB immobilized
in BFA lm was 5 times greater than that of nanoporous RB
lm. A BFA lm of palladium-containing polymer also showed
excellent catalytic activity.547 Karthaus et al. rst adsorbed
photocatalytic TiO2 nanocrystals onto surface-functionalized
and cross-linked BFA lms.548 After calcination, BFA lms of
TiO2 nanocrystals were obtained. Owing to the porous
structure, the TiO2 BFA lms showed a photocatalytic activity
6.8 times higher than those of at TiO2 lms when
decomposing a cyanine dye in aqueous solution. In another
work, Rodriguez-Herna ndez et al. incorporated bioactive
compound of alkaline phosphatase (ALP) on the BFA lms
by layer-by-layer technique.549 The BFA lms always showed
higher catalytic activity than that of plate surfaces. More
importantly, ALP was selectively deposited inside the pores in
the case of only the pore wall containing carboxylic acid groups,
allowing the potential applications as microreactors. Huh et al.
prepared patterned stimuli-responsive hydrogel lms of poly-
(acrylic acid) (PAA) and PNIPAm using BFA lm as a
template.550,551 The hydrogel lms were then used to reversibly
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adsorb Ag NPs. Depending on the pH responsiveness of PAA,
at lower pH, the PAA hydrogel was hydrophobic and adsorbed
Ag NPs, whereas at higher pH, the hydrogel became
hydrophilic and released Ag NPs. Importantly, the PAA
hydrogel showed an oscillatory performance of adsorption
desorption with a periodically changed pH, demonstrating the
rapid and reversible response to external stimuli (Figure 65).
Due to the thermosensitivity of PNIPAm, the patterned lms
showed a rapid and reversible adsorptiondesorption of Ag
NPs with changes in temperature.
Figure 65. (ac) pH oscillation patterns at various ratios of
[HCO3]0/[H2SO4]0 in the pH oscillatory system of CaSO3
H2O2NaHCO3H2SO4. [HCO3]0/[H2SO4]0 corresponds to (a)
0.5, (b) 1.0, and (c) 2.0. (d, e, f) Oscillations of the adsorption
desorption of Ag NPs occurring at the hydrogel surface derived by the
pH oscillations of (a), (b), and (c), respectively.551 Reprinted from ref
551. Copyright 2013 American Chemical Society.
Figure 66. (a) SEM image of CNT eld emitter after calcination. (b) Plot of the emission current density of CNT BFA lms versus applied electrical
eld. (c) FowlerNordheim plot representing the conventional eld-emission behavior of CNT emitters.436 Reprinted with permission from ref 436.
Copyright 2008 Royal Society of Chemistry.
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Review
The pH response of PAA was also utilized to actuate the
conductivity of a porous semiconductor interface that was
obtained by assembling CNTs on the surface of BFA lm
through sequential layer-by-layer (LBL) deposition.552 Inves-
tigation of the electronic properties revealed that the electrical
conductivity of the interface depended on the connectivity
rather than the amount of CNTs on the surface of the BFA
lms. The conductivity of the lm was dependent on the pH.
When the pH was close to the pKa of PAA, the PAA chains
were swollen, leading to an expansion of the polymer gaps
between CNT laments. As a result, the conductivity of the lm
decreased. The highest conductivity was obtained at pH 1.
Kim et al. conrmed the high electrical conductivity and
excellent eld-emission properties of BFA lms made of
CNTs.436 This BFA lm was prepared with a BF process using
entangled CNTs and a PS blend solution, followed by
pyrolyzing PS (Figure 66a). The surface resistance was
decreased from 137 to 4.3 k/ after calcination, indicating
ecient connectivity of the CNTs. The obtained BFA substrate
of the CNTs demonstrated excellent eld-emission properties
with a turn-on eld of 1.79 V m1 at an emission current
density of 10 A cm2 and a current density of 450 A cm2 at
an electric eld of 2.8 V m1 (Figure 66b,c). These
performances were comparable with those of CNT eld
emitters grown by CVD.
Hou et al. combined the Rayleigh instability technique and
the BF method and prepared porous bead-on-string (BOS)
bers with epoxy E-44.553 A variety of BOS bers with dierent
microstructures that were smooth, less porous, homogeneously
porous, gradiently porous, and dented could be easily prepared
by controlling the experimental conditions, such as the reaction
time, temperature, and humidity (Figure 67ac). The authors
found that the BOS ber could be used for fog harvesting. Due
to the Laplace force and the wettability force induced by the
ellipsoid shape, the gradient-porous BOS bers exhibited better
water-collecting capacity compared with the smooth and
homogeneous porous BOS counterparts (Figure 67df).
Bormashenko et al. demonstrated that BFA lms had the
potential for use in low-voltage electrowetting.60 After a BFA
lm of PC was impregnated with silicone, the onset of
reversible electrowetting occurred at voltages as low as 35 V.
Heng et al. demonstrated a photoelectric cooperative induced
patterned wetting on a hydrophobic BFA lm.554 In this
process, BFA lms of 149 (Scheme 38) were rst modied with
a photosensitive dye of cis-bis(4,4-dicarboxy-2,2-bipyridine)
dithiocyanato ruthenium(II) (N3) by dip-coating method and
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Figure 67. (ac) SEM images of the polymer BOS bers with smooth
(a), homogeneously porous (b), and gradient-porous (c) micro-
structures. (df) Aggregation of water droplets on a polymer of BOS
bers with dierent microstructures: (d) smooth, (e) homogeneously
porous, and (f) gradient porous.553 Reprinted with permission from ref
553. Copyright 2013 Royal Society of Chemistry.
Scheme 38. Chemical Structure of Polymer (149)
subsequently treated with hydrophobic heptadecauorodecyl-
trimethoxysilane (FAS) vapor, producing photosensitive and
hydrophobic BFA lms. The wetting threshold voltage of the
BFA lm was about 24.9 V without light, and it decreased to
about 10.8 V with light because of the photoconductity
property. Relying on this dierence of threshold voltages with
and without light, photoelectric cooperative induced patterned
wetting was achieved with assistance of a photo mask.
Another study revealed that BFA lm could be used as a
strongly adhesive surface for water droplets, and the adhesive
force could be controlled by the pore diameter and density.555
8. CONCLUSION
The preparation of highly ordered porous lms using the BF
method is another example of humans devising a technique
inspired by nature. The seemingly simple process endows the
resulting lms with both an ordered surface structure and
patterned distributions of functional groups on the surface,
which provides more opportunities to further modify and
functionalize the lms, thus broadening their applications. After
two decades of development, this technique has now made a
large impact in the area of materials and has created a general
interest that has extended to a large scientic community at the
frontiers of chemistry, physics, biology, and medicine. The BF
technique has particularly aroused the interest of industry. A
recent patent by the Fuji Film Co. demonstrated their interest
in equipment that could produce BFA lms continuously on a
commercial scale.18
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However, several challenges remain before we can push the
BF technique into real practical applications. The rst challenge
is how to make very small and very large pores reliably from
arbitrary polymeric and nonpolymeric materials. To address
this issue, an unambiguous elucidation of the mechanism of
BFA formation is needed, as is the exploitation of novel BF
methods. Although great eorts have been made to expose the
BF mechanism, there are many conicts and puzzles, including
the nucleation and growth process of the droplets on the
polymer solution, the interaction between the polymer solution
and the water-droplet template, the stabilization of droplets,
and the driving force behind the droplet arrangement. The
clarication of these confounding details will benet the
development of new BF methods and improve the control of
pore size. The second challenge is how to precisely control the
surface morphology of the BFA to rival the expensive
lithography technique for a variety of pore shapes and
arrangements. The physical deformation techniques, such as
mechanical stretching or shrinking and photomanipulation,
oer a simple strategy to construct BFA lms with novel pore
shapes.38,277,315 However, these techniques are only available
for certain types of polymers. Therefore, developing new
manipulation methods is essential in future research. The last
challenge is how to further exploit the new functions and
applications of BFA lms. To achieve this goal, apart from
making progress in solving the above two problems, we must
exploit new functional materials in the BF process and devise
novel postmodication methods to expand the functions of
BFA lms.
In summary, the recent rapid development of the BF method
has demonstrated its merits of low cost, easy operation, and
wide application scope. Furthermore, the complexity of BF that
emerges from the relationship between experimental parame-
ters and its morphology compels us to discover more novel
physical details of the process. We believe breakthroughs in
both fundamental and practical aspects will be achieved upon
better understanding the formation mechanism and with the
development of new materials.
AUTHOR INFORMATION
Corresponding Author
*E-mail: lilei@xmu.edu.cn. Tel: +86-592-2186296. Fax: +86-
592-2183937.
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval.
Notes
The authors declare no competing nancial interest.
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Biographies
Aijuan Zhang received her B.E. (2008) and M.S. degrees (2011) from
Xiamen University and Nankai University, respectively. She is
currently a Ph.D. candidate at the College of Materials, Xiamen
University, under the supervision of Prof. Lei Li. Her research interests
are macromolecular self-assembly and porous materials.
Hua Bai received his B.S. (2004) and Ph.D. (2009) degrees in
Department of Chemistry at Tsinghua University, under the
supervision of Prof. Gaoquan Shi. From 2009 to 2011 he was a
postdoctoral fellow in the Department of Chemical Engineering at
Tsinghua University. He is currently an associate professor in the
College of Materials at Xiamen University. His research interests
mainly focus on organic conjugated materials, solar cells, and
graphene.
Lei Li received his Ph.D. in 2001 from China Textile University. After
two-year postdoctoral experience at Peking University, he joined the
National Institute of Advanced Industrial Science and Technology
(AIST) in Japan as a NEDO and JSPS research fellow. In 2007 he
BB
Review
moved to the College of Materials, Xiamen University, as a full
professor. He was a visiting scholar at the University of Akron in 2013.
His research interests are living radical polymerization, functional
polymers, and porous materials.
ACKNOWLEDGMENTS
L.L. gratefully acknowledges the National Natural Science
Foundation of China (Nos. 51373143 and 21174116), the
Natural Science Foundation of Fujian Province (No.
2014J0105), and the Fundamental Research Funds for the
Central Universities (Nos. 2013SH003 and 201312G004).
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BP DOI: 10.1021/acs.chemrev.5b00069
Chem. Rev. XXXX, XXX, XXXXXX