Colloids and Surfaces A: Physicochem. Eng.

Aspects 506 (2016) 782788

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Selective assembly of silver nanoparticles on honeycomb lms and

their surface-enhanced Raman scattering
Hai-yan Chen a,b , Jun-liang Liu a , Wei-chao Xu a , Zhi-feng Wang a , Cheng-yin Wang a, ,
Ming Zhang a,c,
a
College of Chemistry and Chemical Engineering, Key Laboratory of Environmental Material and Environmental Engineering of Jiangsu Province, Yangzhou
University, Yangzhou 225002, China
b
Yangzhou Polytechnic College, Yangzhou 225127, China
c
Test Center, Yangzhou University, Yangzhou 225009, China

h i g h l i g h t s

g r a p h i c a l

a b s t r a c t

Honeycomb lms of PS-b-PAA were

fabricated by breath gure method.

Ag NPs were selectively assembled

on the surface of honeycomb lms
rather than in the pores.
The concentrations of precursors
were important to the amount and
uniformity of Ag NPs.
The hybrid lm decorated with Ag
NPs exhibited strong SERS of R6G
molecules.

a r t i c l e

i n f o

Article history:
Received 16 April 2016
Received in revised form 17 July 2016
Accepted 19 July 2016
Available online 20 July 2016
Keywords:
Breath gure method
Polystyrene-block-polyacrylic acid
Silver nanoparticles
Surface-enhanced Raman scattering

a b s t r a c t
A facile approach to selective assembly of Ag nanoparticles on honeycomb lm and their highly sensitive surface-enhanced Raman scattering of rhodamine 6G molecules were described. Honeycomb lms
were prepared based on amphiphilic block polymer (polystyrene-block-polyacrylic acid), by breath gure method. Key inuencing factors to control micropore size and tune lm surface properties, such
as polymer concentration, solvent, relative humidity and substrate, were investigated. Ag nanoparticles
were selectively assembled on the surface of honeycomb lms rather than in the pores. The Ag nanoparticles on the hybrid lms were applied in surface-enhanced Raman scattering of rhodamine 6G molecules
to dramatically enhance signals. This proposed approach opens a new route for selective modication
of honeycomb lms and provides a facile and effective method for preparing surface-enhanced Raman
scattering substrates.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Corresponding author at: College of Chemistry and Chemical Engineering, Key
Laboratory of Environmental Material and Environmental Engineering of Jiangsu
Province, Yangzhou University, Yangzhou 225002, China.
Corresponding author.
E-mail addresses: wangcy@yzu.edu.cn (C.-y. Wang), lxyzhangm@yzu.edu.cn
(M. Zhang).
http://dx.doi.org/10.1016/j.colsurfa.2016.07.043
0927-7757/ 2016 Elsevier B.V. All rights reserved.

As an important technology in modern testing eld, surface

enhanced Raman scattering (SERS) technique is widely applied in
chemical industrial analysis, biological analysis, medical detection
and many other areas due to its high sensitivity, good selectiv-

H.-y. Chen et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 506 (2016) 782788

ity and nondestructive testing of samples [19]. Constructing SERS

substrates with high activity is one of important subjects in SERS
studies. It is believed that substrates with ordered structures are
superior to disordered nanostructures [6,7,1012]. Most of these
attractive advantages are based on the periodic arrays of nanoparticles (NPs), which possess maximized specic surface density of
hot spots and higher surface enhancement factors. Several methods
have been applied to fabricate ordered SERS substrates including
laser micro-nano processing, templating techniques, lithography
and so on [6,1215]. However, these commonly used SERS substrate
preparation methods are time-consuming and high equipment
costs. Therefore, the patterning technique known as breath gure method was also introduced due to its simple, inexpensive,
and robust mechanism of pattern formation [1619]. This method
was rst reported by Francoise et al. in 1994 [20]. By casting polymer solutions under humid conditions, the breath gure method
makes use of the condensed water droplets as dynamic templates
to produce ordered pores within a size range of 300 nm to 20 m
[2123]. The versatility of this technique has also been demonstrated by the preparation of hybrid organic/inorganic structures
[2426]. For example, ordered honeycomb lms containing Au
NPs were prepared and presented a strong SERS of rhodamine
6G (R6G) [27]. Hirai et al. described a simple preparation method
for silver pincushion lms involving the breath gure method and
vapor deposition processes and measurements of SERS on the silver pincushion lms [15]. Raman spectra demonstrated that the
obtained SERS substrate could detect R6G at concentrations as low
as 0.5 nM. It was found that more ordered honeycomb lms resulted
in stronger SERS. Wan and co-workers also developed an approach
to prepare highly sensitive SERS substrates with honeycomb lms
decorated by Ag NPs [28]. But Ag NPs in this method could be found
both on the external surface and in the pores of honeycomb lms,
which meant selective assembly of NPs on patterned porous surface
was not achieved.
As a versatile and efcient method of fabricating highly ordered
pore arrays, the breath gure method has raised continuing concern
in optical and optoelectronic devices, electrode materials, separation and biology over recent decades [2936]. Amphiphilic block
copolymers, which have a high segment density in some selective
solvent, can be gathered in the interface layer of organic solvent
and water so as to effectively stabilize the water droplets and prevent the mutual cohesion between the water droplets. Amphiphilic
block copolymers as excellent candidates and functional materials
are considered to be a kind of ideal materials for preparing ordered
porous lms. Honeycomb porous lms have been employed as templates not only to fabricate patterned architectures but also for the
assembly of nanoparticles. Sun et al. presented an elegant way to
tune the localization of SiO2 NPs inside a highly structured honeycomb lm depending on the NPs surface functionalization [37];
A one-step procedure was also demonstrated for the preparation
of nanoparticles-decorated lms by casting a mixed solution of
polystyrene and CdSe nanoparticles [38]. CdSe nanoparticles can
self-assemble and segregate at the polymer solutionwater droplet
interface; Wu and co-workers described a facile approach for honeycomb structures of Mn-12 single-molecule magnets [39] and
surfactant-encapsulated polyoxometalate complexes [40]. As for
above mentioned strategies, NPs were successfully decorated in the
pores of honeycomb lms. As far as SERS substrates are concerned,
only the NPs assembled on the surface can lead to the best effect.
However, researches on selective assembly of NPs on the honeycomb patterned porous surface and their applications in SERS have
not been reported.
In this paper, a typical amphiphilic block polymer, polystyreneblock-polyacrylic acid (PS-b-PAA), was selected to fabricate
honeycomb patterned porous lms by breath gure method. Several key inuencing factors, such as the concentration of polymer,

783

the relative humidity of the atmosphere, the properties of solvent,

the spreading volume and the substrates, were investigated for controlling micropore size and tuning lm surface properties. Ag NPs
with 20100 nm were successfully assembled on the external surface of the porous lms based on chemical deposition method. The
hybrid lms decorated with Ag NPs exhibited strong SERS effect of
R6G molecules. To the best of our knowledge, it is the rst report
on the selective assembly of Ag NPs on the external surface of the
honeycomb patterned porous lm. This proposed approach opens
a new route for selective modication of patterned porous lms
and provides a facile and effective method for preparing SERS substrates.
2. Experimental section
2.1. Materials
The synthesis of PS-b-PAA by atom transfer radical polymerization (ATRP) was described as reported [41]. The relative molecular
weights of PS and PAA blocks were 12500 and 1000 gmol1 ,
respectively. The PDI of such diblock copolymer was 1.09. Hydrogen
peroxide (H2 O2 , 30 wt%), sulfuric acid (H2 SO4 , 98 wt%), formaldehyde (HCHO, 36 wt%), ammonia (17 wt%), silver nitrate (AgNO3 ),
and rhodamine 6G (R6G) and chloroform (CHCl3 ) were purchased
from Sinopharm Chemical Reagent Co. Ltd. (Shanghai, China). They
were used as received without further purication. All the other
reagents used were analytical grade. Deionized water was obtained
by purication through a Millipore water system and was used
throughout. All the experiments were conducted at room temperature.
2.2. Preparation of the honeycomb-patterned polymer lms
The honeycomb-patterned lms were prepared by the breath
gure method and the schematic illustration including the set-ups
for fabricating the porous polymer lms was shown as Fig. 1. The
glass substrate was immersed in a piranha solution (98% H2 SO4 /30%
H2 O2 , volume ratio, 3:1) for 30 min, and then rinsed with deionized
water and ethanol before lm fabrication, respectively. PS-b-PAA
was dissolved in CHCl3 with a concentration ranging from 2 to
50 mg/mL. Then, 10 L PS-b-PAA solution was dropped onto a clean
glass substrate at room temperature in a chamber in which the relative humidity could be controlled by bubbling through distilled
water and measured by a Humidity & Temperature Meter (AR-847,
Smart Sensor). After the solvent evaporated completely, honeycomb lms were obtained. For comparison, the at lms without
pores were obtained using the same procedure under ambient condition.
2.3. Selective assembly of Ag NP on honeycomb-patterned lms
The assembly of Ag NPs on the external surface of the
honeycomb-patterned porous lms was accomplished by chemical deposition onto the lms. A piece of as-prepared lm was rst
immersed into AgNO3 aqueous solution with different concentra-

Fig. 1. Schematic illustration including the set-ups for fabricating the porous polymer lms.

784

H.-y. Chen et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 506 (2016) 782788

tions. Then 5 mL 1% ammonia solution was added by dropwise into

a vessel. Subsequently 5% formaldehyde solution was added as a
reductant, and the reaction was kept for 30 min under stirring at
room temperature. Finally, honeycomb hybrid lm decorated with
Ag NPs was taken out and dried at room temperature.
2.4. Measurements of surface-enhanced Raman scattering
Samples for SERS measurements were prepared by dropping
10 L R6G ethanol solution with different concentrations onto the
as-prepared hybrid lms decorated with Ag NPs. Raman spectra
were measured using a Britain Renishaw Invia Raman spectrometer with a solid-state laser (excitation at 532 nm, 35 mW) at room
temperature in the range of 1800400 cm1 .
2.5. Characterization
Morphology of the as-prepared samples was observed by using
FE-SEM (Hitachi, S-4800, 15 kV). The electron gun voltage was set
at 15 kV, and the sample surface was sputter coated with gold to
achieve a better quality of the secondary electron images under
the electron beam. X-ray diffraction (XRD) patterns were recorded
on a Bruker AXSD8 ADVANCE X-ray diffractometer at room temperature. The water contact angle was analyzed by OCA40 optical
contact angle measurements (DataPhysics, Germany), using the
sessile water droplet method. A water droplet size of 3 mL was used
for OCA measurements.

3. Results and discussion

3.1. Inuence of substrates, humidity and polymer concentration
on the morphology of honeycomb lms
Honeycomb lms were prepared by breath gure method, and
using PS-b-PAA in CHCl3 at 25 C under high relative humidity. Different substrates were employed to fabricate such microporous
lms. As observed by SEM in Fig. 2, the highly ordered polymer
lms with a few hundred nano-meter pore size were easy to be
fabricated on both common glass slide (Fig. 2a) and ITO conductive
glass (Fig. 2b).
It is generally considered that humid atmosphere, which could
be provided by static humid atmosphere or controlled by adjusting the air ow rate, is an essential parameter for breath gure
method [42]. The use of humid airow instead of static conditions should make solvent evaporation easier and allow breath
gures generation even for solvents with a relatively high boiling
point. Herein high relative humidity was controlled by adjusting
the air ow rate. Fig. 3 shows SEM images of the porous lms prepared from PS-b-PAA solutions in CHCl3 under different relative
humidity. It can be clearly seen that the pore sizes increased from
0.68 m (Fig. 3b) to 1.96 m (Fig. 3e) with an increase of relative
humidity from 55% to 85%. This is mainly due to the fact that the
pore size and periodicity of polymer lm are determined by the
size and volume of the water droplets which are increased with
relative humidity. It was interesting that there was only transpar-

Fig. 2. SEM images of the honeycomb lms prepared from PS-b-PAA solutions in CHCl3 at different substrates (a) common glass slide, (b) ITO glass, Other conditions:
humidity: 75% RH, concentration: 10 mg/mL, spreading volume: 10 L. Insets show water droplet proles and contact angles on the lm.

Fig. 3. SEM images of the honeycomb lms prepared from PS-b-PAA solutions in CHCl3 at different humidity (a) <50%, (b)55%, (c) 65%, (d) 75%, (e) 85% (f) >90%. Other
conditions: concentration: 10 mg/mL, spreading volume: 10 L.

H.-y. Chen et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 506 (2016) 782788

ent lm and no pores were observed under relative humidity less

than 50% (Fig. 3a), which conrmed that the water droplet array
as a template was a critical parameter for breath gure formation.
Fig. 4 shows the dependence of the pore size on the polymer
concentration. The average pore size of polymer lms decreased
from 1.5 m to 0.77 m with the increase of polymer concentration
from 2 mg/mL (Fig. 4a) to 50 mg/mL (Fig. 4c). Such tendency can be
attributed to the fact that higher concentration of polymer solution
can increase the viscosity of the solution. The higher viscosity is
favored for slower growth of the water droplets and faster polymer

785

precipitation at the water droplet interface, consequently resulting

in the formation of smaller pores.

3.2. Mechanism of selective assembly of Ag NPs on honeycomb

patterned lms
The as-prepared porous PS-b-PAA lms were employed as template to direct the assembly of Ag NPs by chemical deposition. The
morphology of selective assembly of Ag NPs on the honeycombpatterned lms can be clearly seen in Fig. 5. It was obvious that Ag
NPs assembled preferentially on the external surface of the lm,

Fig. 4. SEM images of the honeycomb lms prepared from PS-b-PAA solutions in CHCl3 at different concentrations (a) 2, (b) 10, (c) 50 mg/mL. Other conditions: humidity:
75%, spreading volume: 10 L.

Fig. 5. (a) SEM image of Ag NPs assembled on the surface of honeycomb lm; (b) part of the top surface was removed using an adhesive tape after lling; (c) cross-sectional
image of the honeycomb-patterned hybrid lm.

Fig. 6. SEM images of Ag NPs assembled on the surface of honeycomb lms at different AgNO3 concentrations (a) 2, (b) 5, (c) 20, (d) 50 mM.

786

H.-y. Chen et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 506 (2016) 782788

and none of them were in the pores. This phenomenon can be

attributed to the cooperating effects of both electrostatic adsorption and hydrophobic force of PS-b-PAA lm. It has been pointed
out that the PS porous lms or even PS-based amphiphilic block
copolymer lms are of hydrophobic surface and hence water dispersion of particles is not wet on them [43,44]. As shown in inset
Fig. 2a the contact angles value of honeycomb PS-b-PAA lms was
about 121 and this result also conrmed that PS-b-PAA porous
lm was hydrophobic, which meant the highly porous lm could
entrap air in the pores and prevent the pores from being wetted by
water. When the honeycomb lm was immersed into the precursor solution, there was electrostatic adsorption between negative
PS-b-PAA and electron-decient Ag+ . Meanwhile, a reduction of
the coordinated Ag+ in aqueous HCHO solution generated Ag NPs
which were preferentially deposited on the external surface due
to the hydrophobicity of the lm. When the amount of reducing
agent HCHO increased gradually, the original trace Ag NPs could
be used as silver crystal nucleus and induced subsequent silver to
continuously grow on the external surface, consequently resulting in selective assembly of Ag NPs on the whole honeycomb
lm.
During the process of deposition and selective assembly of
Ag NPs, controlling the concentration of AgNO3 solution is a key
step. As shown in Fig. 6, there is an increase in both number
and size of Ag NPs with the increase of AgNO3 concentration.
The average diameter of Ag NPs is in the range of 20100 nm
when the concentration of AgNO3 solution is below 50 mM. It is
believed that Ag NPs are suitable for SERS in the range of 5100 nm
[45].
The XRD patterns of the products obtained before and after decorating Ag NPs are shown in Fig. 7. After decorating Ag NPs, four
diffraction peaks corresponding to the (111), (200), (220), and (311)
crystalline planes of sliver are present at 2 = 38.1 , 44.2 , 65.5 , and
77.2 respectively, which conrmed the formation of Ag NPs.
For comparing and analyzing the inuence of honeycomb structure on the morphology of Ag NPs, at PS-b-PAA lms without pores
were prepared for deposition of Ag NPs based on the same procedure. The morphology of Ag NPs on at PS-b-PAA lm is shown
in Fig. S1 in the Supporting information. Not only the small Ag
NPs (about 50 nm) non-selectively close-packed onto the surface,

Fig. 7. XRD pattern of hybrid lms decorated with Ag NPs at different AgNO3 concentrations (a) 50, (b) 5, (c) 0 mM.

but also the large particles (hundreds nanometers) were randomly

present.
3.3. Surface enhanced Raman scattering performance
R6G was used as Raman probes to evaluate SERS of the hybrid
lms decorated with Ag NPs. Fig. 8 shows Raman scattering spectra from 50, 5, and 0.5 nM R6G solutions on honeycomb and at
lms with Ag NPs (keeping the concentration of AgNO3 is 20 mM).
Clear Raman scattering peaks could be observed when honeycomb lms with Ag NPs were used. The peaks at 809, 916, 1180,
1371, 1591 and 1624 cm1 are the characteristic Raman lines of
R6G molecule. However, no specic peaks were detected in the
case of the at lm with Ag NPs. It can be ascribed to the serious aggregation of Ag NPs and large particle size over 100 nm
on at lm substrate (Fig. S1 in the Supporting information). The
main difference between our selective deposition and the nonselective deposition of silver nanoparticles is the orderly structures,
which also increases the number of immobilized Ag nanoparitlces.
These together make contributions to the enhancement of surfaceenhanced Raman scattering (SERS) signals. A similar phenomenon
is reported in Au assembly [27]. Meanwhile, the uorescence background increased when 50 nM R6G solution was used. In this
experiment, the obtained surface-enhanced Raman scattering sub-

Fig. 8. Raman spectra of R6G with different concentration on honeycomb and at lms decorated with Ag NPs (keeping the concentration of AgNO3 is 20 mM).

H.-y. Chen et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 506 (2016) 782788

787

Acknowledgments
This work is nancially supported by the National Natural Science Foundation of China (51273172, 21375116, 51403181), a
project funded by the Priority Academic Program Development of
Jiangsu Higher Education Institutions and Jiangsu Province research
program on analytical methods and techniques on the shared platform of large-scale instruments and equipment (BZ 201409). Some
apparatus used for characterization was provided by testing center
of Yangzhou University. This work is also nancially supported by
the Open Foundation of Key Laboratory of Environmental Materials
and Engineering of Jiangsu Province (K13073).
Fig. 9. Raman spectra of R6G at 106 M concentration adsorbed on honeycomb
hybrid lms obtained from different AgNO3 concentrations (a) 2, (b) 5, (c) 20, (d)
50 mM.

strate could be applied to detect R6G at concentrations as low as

0.5 nM. This result was as good as one in early reported article
[12].
As we all know, the SERS effect of substrates on the absorbed
analyte molecules depends on the size and density of noble metal
NPs [4548]. In order to investigate the inuence of Ag NPs with
different size and density on the SERS performance, a series of SERS
experiments based on as-prepared samples with different AgNO3
concentration were also carried out. Fig. 9 shows the SERS spectra of
R6G at 106 M concentrations adsorbed on honeycomb hybrid lms
obtained from different AgNO3 solution. The results showed that
with the increase of AgNO3 concentration the spectral intensities
increased at rst and then decreased. When AgNO3 concentration
was below 20 mM, the spectral intensities were increased with the
increase of Ag NPs, which resulted from the increasing concentration of AgNO3 solution. However, it was observed that the SERS
signal became weakened when the AgNO3 concentration reached
50 mM (Fig. 9, curve d). This phenomenon could be ascribed to the
different aggregation of Ag NPs (Fig. 6), which had great impact on
the SERS activity. The SERS signal was mainly affected by the Raman
hot spots. More Ag NPs produced more Raman hot spots, which
enhanced the SERS signal. However, if the AgNO3 concentration
was too high, both the size and density of Ag NPs became excessive
and aggregation of Ag NPs was inevitable. Due to the aggregation of
Ag NPs, the number of gaps between neighboring Ag NPs decreased
and Raman hot spots would reduce, which resulted in a decline
of the SERS signal. Apparently, the density and size of Ag NPs on
honeycomb lms determine the SERS performance.

4. Conclusions
A simple method was presented for preparing ordered surfaceenhanced Raman scattering substrates by combining the breath
gure method and chemical deposition of Ag NPs. It is the rst
report on the selective assembly of Ag NPs preferentially on the
external surface of the honeycomb patterned porous lm rather
than in the pores. Results indicate that the hybrid lm decorated
with Ag NPs, exhibits strong surface-enhanced Raman scattering
of R6G molecules and the concentration of AgNO3 is crucial to the
uniformity and amount of Ag NPs, which in turn have a signicant
effect on the enhancement factor. In our experiment the obtained
surface-enhanced Raman scattering substrate could detect R6G at
concentrations as low as 0.5 nM. This proposed approach opens a
new route for selective modication of patterned porous lms and
provides a facile and effective method for preparing high-quality
SERS substrates.

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.colsurfa.2016.07.
043.
References
[1] M. Fan, G.F. Andrade, A.G. Brolo, A review on the fabrication of substrates for
surface enhanced Raman spectroscopy and their applications in analytical
chemistry, Anal. Chim. Acta 693 (2011) 725.
[2] B. Sharma, R.R. Frontiera, A.I. Henry, E. Ringe, R.P. Van Duyne, SERS: materials,
applications, and the future, Mater. Today 15 (2012) 1625.
[3] J. Ge, Y. Li, J. Wang, Y. Pu, W. Xue, X. Liu, Green synthesis of graphene quantum
dots and silver nanoparticles compounds with excellent surface enhanced
Raman scattering performance, J. Alloys Compd. 663 (2016) 166171.
[4] Q. An, P. Zhang, J.M. Li, W.F. Ma, J. Guo, J. Hu, C.C. Wang, Silver-coated
magnetite-carbon core-shell microspheres as substrate-enhanced SERS
probes for detection of trace persistent organic pollutants, Nanoscale 4 (2012)
52105216.
[5] H. Hu, Z. Wang, S. Wang, F. Zhang, S. Zhao, S. Zhu, ZnO/Ag heterogeneous
structure nanoarrays: photocatalytic synthesis and used as substrate for
surface-enhanced Raman scattering detection, J. Alloys Compd. 509 (2011)
20162020.
[6] J.A. Huang, Y.Q. Zhao, X.J. Zhang, L.F. He, T.L. Wong, Y.S. Chui, W.J. Zhang, S.T.
Lee, Ordered Ag/Si nanowires array: wide-range surface-enhanced Raman
spectroscopy for reproducible biomolecule detection, Nano Lett. 13 (2013)
50395045.
[7] G. Lu, H. Li, C. Liusman, Z.Y. Yin, S.X. Wu, H. Zhang, Surface enhanced Raman
scattering of Ag or Au nanoparticle-decorated reduced graphene oxide for
detection of aromatic molecules, Chem. Sci. 2 (2011) 18171821.
[8] W. Zhao, Z. Xu, T. Sun, S. Liu, X. Wu, Z. Ma, J. He, C. Chen, Carbon cloth
surface-decorated with silver nanoparticles for surface-enhanced Raman
scattering, J. Alloys Compd. 584 (2014) 635639.
[9] Q. Huang, J. Wang, W. Wei, Q. Yan, C. Wu, X. Zhu, A facile and green method
for synthesis of reduced graphene oxide/Ag hybrids as efcient surface
enhanced Raman scattering platforms, J. Hazard. Mater. 283 (2015) 123130.
[10] A. Snchez-Iglesias, P. Aldeanueva-Potel, W. Ni, J. Prez-Juste, I.
Pastoriza-Santos, R.A. Alvarez-Puebla, B.N. Mbenkum, L.M. Liz-Marzn,
Chemical seeded growth of Ag nanoparticle arrays and their application as
reproducible SERS substrates, Nano Today 5 (2010) 2127.
[11] R.A. Tripp, R.A. Dluhy, Y. Zhao, Novel nanostructures for SERS biosensing,
Nano Today 3 (2008) 3137.
[12] S. Yang, W. Cai, L. Kong, Y. Lei, Surface nanometer-scale patterning in realizing
large-scale ordered arrays of metallic nanoshells with well-dened structures
and controllable properties, Adv. Funct. Mater. 20 (2010) 25272533.
[13] Z. Zhang, F. Xu, W. Yang, M. Guo, X. Wang, B. Zhang, J. Tang, A facile one-pot
method to high-quality Ag-graphene composite nanosheets for efcient
surface-enhanced Raman scattering, Chem. Commun. 47 (2011) 64406442.
[14] R.G. Freeman, K.C. Grabar, K.J. Allison, R.M. Bright, J.A. Davis, A.P. Guthrie, M.B.
Hommer, M.A. Jackson, P.C. Smith, D.G. Walter, M.J. Natan, Self-assembled
metal colloid monolayers: an approach to SERS substrates, Science 267 (1995)
16291632.
[15] Y. Hirai, H. Yabu, Y. Matsuo, K. Ijiro, M. Shimomura, Arrays of triangular
shaped pincushions for SERS substrates prepared by using self-organization
and vapor deposition, Chem. Commun. 46 (2010) 22982300.
[16] A.S. de Leon, A. del Campo, M. Fernandez-Garcia, J. Rodriguez-Hernandez, A.
Munoz-Bonilla, Hierarchically structured multifunctional porous interfaces
through water templated self-assembly of ternary systems, Langmuir 28
(2012) 97789787.
[17] P. Escal, L. Rubatat, L. Billon, M. Save, Recent advances in
honeycomb-structured porous polymer lms prepared via breath gures, Eur.
Polym. J. 48 (2012) 10011025.
[18] S.N. Kengo Manabe, Seimei Shirator, Porous surface structure fabricated by
Breath Figures that suppresses Pseudomonas aeruginosa biolm formation,
ACS Appl. Mater. Interfaces 5 (2013) 1190011905.

788

H.-y. Chen et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 506 (2016) 782788

[19] X.Y. Li, Q.L. Zhao, T.T. Xu, J. Huang, L.H. Wei, Z. Ma, Highly ordered
microporous polystyrene-b-poly (acrylic acid) lms: study on the inuencing
factors in their fabrication via a static breath-gure method, Eur. Polym. J. 50
(2014) 135141.
[20] G. Widawski, M. Rawiso, B. Francois, Self-organized honeycomb morphology
of star-polymer polystyrene lms, Nature 369 (1994) 387389.
[21] C. Wang, D. Wang, X. Hu, G. Wang, Interface interaction within nanopores in
thin lms of an amphiphilic block copolymer and CTAB, J. Colloid Interface
Sci. 354 (2011) 219225.
[22] L.W. Zhu, Y. Ou, L.S. Wan, Z.K. Xu, Polystyrenes with hydrophilic end groups:
synthesis, characterization, and effects on the self-assembly of breath gure
arrays, J. Phys. Chem. B 118 (2014) 845854.
[23] C. Huang, T. Kamra, S. Chaudhary, X. Shen, Breath gure patterns made easy,
ACS Appl. Mater. Interfaces 6 (2014) 59715976.
[24] V. Vohra, A. Bolognesi, G. Calzaferri, C. Botta, Multilevel organization in hybrid
thin lms for optoelectronic applications, Langmuir 25 (2009)
1201912023.
[25] P. Tang, J. Hao, Formation mechanism and morphology modulation of
honeycomb hybrid lms made of polyoxometalates/surfactants at the
air/water interface, J. Colloid Interface Sci. 333 (2009) 15.
[26] Y. Zhu, R. Sheng, T. Luo, H. Li, J. Sun, S. Chen, W. Sun, A. Cao,
Honeycomb-structured lms by multifunctional amphiphilic biodegradable
copolymers: surface morphology control and biomedical application as
scaffolds for cell growth, ACS Appl. Mater. Interfaces 3 (2011)
24872495.
[27] L. Kong, R. Dong, H. Ma, J. Hao, Au NP honeycomb-patterned lms with
controllable pore size and their surface-enhanced Raman scattering,
Langmuir 29 (2013) 42354241.
[28] Y. Ou, L.Y. Wang, L.W. Zhu, L.S. Wan, Z.K. Xu, In-situ immobilization of silver
nanoparticles on self-assembled honeycomb-patterned lms enables
surface-enhanced raman scattering (SERS) substrates, J. Phys. Chem. C 118
(2014) 1147811484.
[29] L. Heng, X. Meng, B. Wang, L. Jiang, Bioinspired design of honeycomb structure
interfaces with controllable water adhesion, Langmuir 29 (2013) 94919498.
[30] J. Xu, Z. Zhu, H. Xue, Porous polystyrene-block-poly(acrylic acid)/hemoglobin
membrane formed by dually driven self-assembly and electrochemical
application, ACS Appl. Mater. Interfaces 7 (2015) 88528858.
[31] L. Pessoni, S. Lacombe, L. Billon, R. Brown, M. Save, Photoactive, porous
honeycomb lms prepared from Rose Bengal-grafted polystyrene, Langmuir
29 (2013) 1026410271.
[32] M. Pisco, F. Galeotti, G. Quero, A. Iadicicco, M. Giordano, A. Cusano,
Miniaturized sensing probes based on metallic dielectric crystals
self-assembled on optical ber tips, ACS Photonics 1 (2014) 917927.
[33] A.S. de Leon, A. Munoz-Bonilla, A. Gallardo, A. Fernandez-Mayoralas, J.
Bernard, J. Rodriguez-Hernandez, Straightforward functionalization of breath
gures: simultaneous orthogonal host-guest and pH-responsive interfaces, J.
Colloid Interface Sci. 457 (2015) 272280.

[34] L. Li, Y. Zhong, J. Li, J. Gong, Y. Ben, J. Xu, X. Chen, Z. Ma, Breath gure
lithography: a facile and versatile method for micropatterning, J. Colloid
Interface Sci. 342 (2010) 192197.
[35] C. Du, A. Zhang, H. Bai, L. Li, Microsieves with excellent solvent resistance:
cross-linkage of perforated polymer lms with honeycomb structure, ACS
Macro Lett. 2 (2013) 2730.
[36] C. Wang, X. Shao, Q. Liu, Y. Mao, G. Yang, H. Xue, X. Hu, One step fabrication
and characterization of platinum nanopore electrode ensembles formed via
amphiphilic block copolymer self-assembly, Electrochim. Acta 52 (2006)
704709.
[37] W. Sun, Z. Shao, J. Ji, Particle-assisted fabrication of honeycomb-structured
hybrid lms via breath gures method, Polymer 51 (2010) 41694175.
[38] A. Bker, Y. Lin, K. Chiapperini, R. Horowitz, M. Thompson, V. Carreon, T. Xu, C.
Abetz, H. Skaff, A.D. Dinsmore, T. Emrick, T.P. Russell, Hierarchical
nanoparticle assemblies formed by decorating breath gures, Nat. Mater. 3
(2004) 302306.
[39] H. Sun, W. Li, L. Wollenberg, B. Li, L.X. Wu, F.Y. Li, L. Xu, Self-organized
honeycomb structures of Mn-12 single-molecule magnets, J. Phys. Chem. B
113 (2009) 1467414680.
[40] H. Sun, H. Li, L. Wu, Micro-patterned polystyrene surfaces directed by
surfactant-encapsulated polyoxometalate complex via breath gures,
Polymer 50 (2009) 21132122.
[41] Y. Kang, T.A. Taton, Core/shell gold nanoparticles by self-assembly and
crosslinking of micellar, block-copolymer shells, Angew. Chem. 44 (2005)
409412.
[42] C. Wang, Y. Mao, D. Wang, Q. Qu, G. Yang, X. Hu, Fabrication of highly ordered
microporous thin lms by PS-b-PAA self-assembly and investigation of their
tunable surface properties, J. Mater. Chem 18 (2008) 683.
[43] H. Yabu, K. Inoue, M. Shimomura, Multiple-periodic structures of
self-organized honeycomb-patterned lms and polymer nanoparticles
hybrids, Colloids Surf. A 284 (2006) 301304.
[44] B.B. Ke, L.S. Wan, P.C. Chen, L.Y. Zhang, Z.K. Xu, Tunable assembly of
nanoparticles on patterned porous lm, Langmuir 26 (2010) 1598215988.
[45] H. Ko, S. Singamaneni, V.V. Tsukruk, Nanostructured surfaces and assemblies
as SERS media, Small 4 (2008) 15761599.
[46] J.C. Fraire, L.A. Prez, E.A. Coronado, Cluster size effects in the
surface-enhanced Raman scattering response of Ag and Au nanoparticle
aggregates: experimental and theoretical insight, J. Phys. Chem. C 117 (2013)
2309023107.
[47] C.P. Shaw, M. Fan, C. Lane, G. Barry, A.I. Jirasek, A.G. Brolo, Statistical
correlation between SERS intensity and nanoparticle cluster size, J. Phys.
Chem. C 117 (2013) 1659616605.
[48] A.X. Yin, W.C. Liu, J. Ke, W. Zhu, J. Gu, Y.W. Zhang, C.H. Yan, Ru nanocrystals
with shape-dependent surface-enhanced Raman spectra and catalytic
properties: controlled synthesis and DFT calculations, J. Am. Chem. Soc. 134
(2012) 2047920489.