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Facile fabrication of crack-free photonic crystals

with enhanced color contrast and low angle
Cite this: J. Mater. Chem. C, 2017,
5, 8194 dependence†
Bo Yi and Huifang Shen *

The cracking and iridescence properties of photonic crystals (PCs) greatly limit their availability, especially
in the realms of color displays and optical devices. Herein, crack-free amorphous PCs with enhanced
color contrast and low angle dependence were fabricated by the co-assembly of polydopamine-coated
polystyrene core–shell nanoparticles (PS@PDA NPs) and 3-aminopropyltriethoxysilane (APTES) via a
thermal-assisted self-assembly method. The covalent bonds, generated from Schiff base reaction or
Michael addition between polydopamine (PDA) and APTES, successfully counteract the tensile stress that is
Received 10th April 2017, initiated from latex shrinkage during drying, thereby enabling the formation of crack-free PCs. Moreover,
Accepted 25th June 2017 thanks to the light-absorbing nature of PDA, a mussel-inspired melanin, and the amorphous arrays, these
DOI: 10.1039/c7tc01549f as-prepared crack-free PCs miraculously exhibit high visibility and low angle dependent structural colors.
This facile, low-cost and environmentally friendly approach for preparing crack-free amorphous PCs can
rsc.li/materials-c be employed in diverse colloidal sphere systems and may boost the promising applications of PCs.

Introduction system; (2) customizing the substrates of the self-assembly. In

the first respect, typical examples of modulating the composi-
Photonic crystals (PCs), structured materials that present long- tions of the colloidal sphere system prevailingly involve adding
range or short-range spatial order on an optical length scale,1–3 monomers,21,23 polymers24,25 and sol–gel precursors.26,27 And
have attracted tremendous interest worldwide on account of their recent reviews creatively present coordination-bonding crack-
inimitable abilities in light manipulation and as a consequence free PCs by forming metal coordination complexes between
of their enormously promising applications in displays,4–8 colloidal spheres.22,28 On the other hand, the methods of
sensors,9–11 optical devices12–15 and so on. In order to artificially tailoring the substrate for crack-elimination can normally be
fabricate high quality PCs, the bottom-up self-assembly methods realized by employing low-adhesive or patterned substrates29–31
such as vertical deposition,16 drop-casting17 and spray coating18 and assembling at liquid interfaces,32 which would relieve the
are blooming into mainstream approaches for their simplicity adhesion force of the substrate and tensile stress during latex
and low-cost, compared to conventional top-down semiconductor shrinkage. Despite these efforts that have admirably dispelled
techniques.19 Nevertheless, there is an unavoidable barrier cracks from PCs, it should be noted that there remain several
encountered in the construction of PCs, where the self- restrictions for the latent applications of PCs. For instance, the
assemblies of colloidal spheres are prone to cracking through- extra additives might render a poor performance in the optical
out solvent evaporation. Commonly, crack formation is a result properties of PCs,28 and the special substrates will be costly or
of the transverse tensile stress, which is developed from the inappropriate for practical utilization.30,32 Particularly, the
shrinkage of colloidal spheres, exceeding a critical value during structural colors of attained crack-free PC films are usually
the drying process.20–22 whitish under ambient light for light scattering and iridescent
To elude cracking in PCs, a wide variety of strategies have depending on the viewing angle due to the anisotropic opal struc-
been put forth in previous studies, which mainly focus on two ture. Hence, it is necessary to develop a simple and inexpensive
aspects: (1) altering the compositions of the building-block method that endows crack-free PCs with high visibility and low angle
dependent structural colors, which generally require short-range
School of Chemistry and Chemical Engineering, South China University of ordered, or quasi-amorphous, structures.3
Technology, Guangzhou 510640, P. R. China. E-mail: cehfshen@scut.edu.cn
In this work, we describe a facile approach for fabricating crack-
† Electronic supplementary information (ESI) available: The SEM images and size
distributions of PS NPs, optical photographs of PCs, the mode of angle variable
free amorphous PCs with enhanced color contrast and low angle
detection systems, PC films after the hose stream test, and the table of reflection dependence through covalent bonding among modified colloidal
peaks of PCs. See DOI: 10.1039/c7tc01549f spheres. By the co-assembly of 3-aminopropyltriethoxysilane

8194 | J. Mater. Chem. C, 2017, 5, 8194--8200 This journal is © The Royal Society of Chemistry 2017
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(APTES) monomers and polydopamine coated polystyrene Fabrication of crack-free amorphous PC films
nanoparticles (PS@PDA NPs), the APTES monomers containing A simple thermal-assisted self-assembly method was used to
amino groups can react with the benzoquinone structures of attain the crack-free amorphous PC films.34 Prior to use, the
polydopamine (PDA) effortlessly, where covalent bonds are glass slides (24  24 mm) were cleaned by ethanol in an
produced. As the solvent evaporates, APTES monomers will ultrasonic bath for 30 min and dried in a vacuum oven.
self-condense and cross-link, configuring a Si–O–Si network. In PS@PDA core–shell NPs were dispersed in deionized water at
the end, the interaction among PS@PDA NPs can be reinforced
Published on 26 June 2017. Downloaded by Indian Institute of Technology Kanpur on 8/3/2020 11:42:33 AM.

a concentration of 5 wt%, followed by ultrasonication for 1 h.

by covalent bonds, giving rise to crack-free amorphous PCs, in The as-prepared PS@PDA suspension was modified by adding
which the tensile stress has been entirely counterbalanced. an appropriate amount of APTES solution (5 wt%), which
Moreover, owing to the coating of PDA, a mussel-inspired melanin, should be used right after it was diluted. Then the modified
and isotropic amorphous structure, these as-prepared crack- suspension was cautiously cast onto the pre-treated glass slide
free PCs can show high visibility and low angle dependence. and spread uniformly. As the self-assembly process ended by
This discovery may deliver a new route to assemble crack-free placing the glass slide at 45 1C for about 30 min, a crack-free
amorphous PCs and promote the potential applications of PCs amorphous PC film was obtained.
in displays.
Characterization

Experimental The surface morphologies of the PCs were imaged using a field
emission scanning electron microscope (FE-SEM) (Zeiss, LEO-
Materials 1530VP). Before observing, a thin layer of platinum gold was
Styrene (St), methacrylic acid (MAA) and ammonium persulfate sputtered on the film using a sputter coater (Quorum, Q150T ES).
(APS) were purchased from Tianjin Damao Chemical Reagents. The size distributions of PS NPs were measured by dynamic light
Dopamine hydrochloride and tris(hydroxymethyl)aminomethane scattering (Malvern, Zetasizer Nano-ZS ZEN3600). A transmission
(Tris) were purchased from Shanghai Yuanye Bio-Technology Co., electron microscope (TEM) (JEOL, JEM-2100) was used to
Ltd. 3-Aminopropyltriethoxysilane (APTES) was purchased from observe the morphology of PS@PDA NPs. Infrared spectra were
Aladdin Industrial Corporation. Deionized water (18.2 MO cm 1 measured by Fourier transform infrared (FT-IR) spectroscopy
resistivity) was used throughout the experiments. Styrene was (Bruker, TENSOR-27). The X-ray energy dispersive spectrum
purified by decompression distillation to remove polymerization (EDS) was recorded on an Oxford Inca-400 energy dispersive
inhibitors. All other reagents were used without any further spectrometer. Reflection spectra were obtained using an
purification. ultraviolet-visible (UV-vis) spectrophotometer (Hitachi, U-3010).
Photographs of the as-prepared PC films were taken using a
Synthesis of monodispersed polystyrene nanoparticles digital camera (Canon, 1300D).
Monodispersed polystyrene (PS) nanoparticles (NPs) were synthe-
sized via an emulsifier-free emulsion polymerization method
according to the literature.33 In brief, 100 mL of deionized water,
Results and discussion
an appropriate amount of St (4–10 g) and 1 g of MAA were added Homogeneously dispersed PS NPs with various diameters,
to a 250 mL four-necked round-bottomed flask accompanied 162 nm, 186 nm and 252 nm, respectively, were first synthe-
with a mechanical stirring rod, a thermometer and a coiled sized as the core particles through an emulsifier-free emulsion
condenser. When the mixture was heated to 75 1C under a polymerization method. SEM images and size distributions of
stirring rate of 300 rpm, 0.15 g of APS dissolved in 5 g of the three PS NPs are shown in Fig. S1 (ESI†), which illustrates
deionized water was quickly injected into the reactor. The whole that these colloid spheres have a good polydispersity index
experiment was sustained at 75 1C and kept in a nitrogen (PDI) of around 5%, which conforms to the demand of assem-
atmosphere. After 7 h of reaction, the PS latex was obtained. bling high quality photonic crystals.16 Next, benefited from the
Finally, the PS powder was collected by centrifugation and stored unique adhesion capability of PDA, PS@PDA core–shell NPs
in a dryer for the subsequent experiment. were fabricated by directly decorating a PDA shell-layer on the
surface of PS particles, where an in situ self-polymerization
Preparation of PS@PDA core–shell nanoparticles reaction of dopamine (DA) occurred under weakly alkaline
In a typical procedure, PS powder (0.1 g) was redistributed in the conditions (Scheme 1a). In particular, dopamine was primarily
Tris–HCl buffer (50 mL, 10 mM; pH = 8.5) and ultrasonicated for oxidized into the corresponding quinone compounds, which
30 min. Then, 50 mg of dopamine hydrochloride was directly could polymerize into oligomers via intra- or inter-molecular
immersed in the PS dispersion and maintained under mild cross-linking reaction, and then, PDA was attained after the
magnetic stirring for 20 h at ambient temperature. Lastly, the aggregation of oligomers.35,36 With the progress of the reaction,
PS@PDA core–shell NPs were fabricated. Following separation PDA polymerized in the suspension would continuously stick to
by centrifugation and rinsing with deionized water several times, the PS NP surface. The SEM and TEM images of PS@PDA NPs
the PS@PDA NPs were ready for the following co-assembly clearly indicate that the nanoparticles are greatly monodispersed
process. with an average size of 198 nm (Fig. 1a and b). Additionally, the

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Fig. 2 Schematic illustration of the fabrication of crack-free amorphous

PCs and the crack-elimination mechanism.

ethoxy groups (–OCH2CH3), which will hydrolyse to three

Scheme 1 Mechanisms of (a) the polymerization of dopamine, (b) the
silanol groups, –Si(OH)3, once dissolved in water. Throughout
process of reaction between polydopamine and APTES (blue: product of the process of water evaporation, the hydrolysis product of
Schiff base reaction, red: product of Michael addition). APTES monomers would self-condense to oligomers, followed
by generation of the cross-linked APTES polymer. Meanwhile,
under a basic circumstance provided by the amino groups of
APTES, the catechol of the PDA matrix was oxidized into the
corresponding quinone form. And the benzoquinone structures
could immediately react with amino-terminated APTES monomers/
oligomers via Schiff base reaction or Michael addition without
any harsh conditions (Scheme 1b).36,38 As the reaction between
PDA and APTES was accomplished, eventually, the PS@PDA NPs
were successfully bounded together by the Si–O–Si network of
cross-linked APTES polymers. And the PS@PDA/APTES hybrid
was assembled into a crack-free amorphous PC film, where the
adhesion force of the substrate and tensile stress derived from
the shrinkage of colloid spheres were repelled through covalent
bonding. Detailed explanations of how the amorphous structure
forms will be discussed elsewhere.
For the purpose of confirming the formation of PDA and
testifying the reaction that occurred between PDA and APTES,
the comparison of FT-IR spectra of PS NPs, PS@PDA NPs and
the PS@PDA/APTES hybrid has been performed (Fig. 3a). Line 1
Fig. 1 SEM (a) and TEM (b) images of synthesized PS@PDA NPs; the PS is the FT-IR spectrum of pristine PS, which is in great agree-
core size is 186 nm. (c) Photograph of PS and PS@PDA NPs dispersed in
ment with those previously published:33 aromatic C–C bending
deionized water with the concentration of 5 wt%; diameters of the PS/PS
core are 186 nm, 162 nm, 186 nm and 252 nm, from left to right. at 698 cm 1, C–H bending of the benzene ring at 757 cm 1, C–C
stretching of the benzene ring at 1452 cm 1 and 1493 cm 1,
aliphatic C–H stretching at 2922 cm 1 and C–H stretching of
TEM image manifests that slightly bumpy PDA shell layers have the benzene ring at 3026 cm 1. Besides, the wide absorbance
been successfully formed around the PS spheres, which is with a peak around 3444 cm 1 (O–H stretching) and CQO
consistent with the result of previous research.37 To gain more stretching at 1699 cm 1 are due to the existence of –COOH in
insight into the effect of coating a thin PDA layer over PS comonomer MAA. After surface modification with PDA, it
granules, dispersions (5 wt% in water) of pristine PS NPs and evidently shows that the N–H/O–H stretching vibrations are
different core size PS@PDA NPs are displayed in Fig. 1c, which presented as a broad peak around 3425 cm 1, and the signal at
definitely shows that the dispersed PS@PDA NPs can produce 1602 cm 1 might correspond to the N–H bending of PDA (line 2,
diverse colors while the PS latex is milky-white because of light Fig. 3a). Moreover, with the addition of APTES, a characteristic
scattering. absorption peak of 1100 cm 1 can be discerned in line 3 (Fig. 3a),
Fig. 2 demonstrates the self-assembly of crack-free amor- which is in accordance with the asymmetric stretching of
phous PCs. Initially, monodispersed PS@PDA core–shell NPs Si–O–Si bonds and implies the successful self-condensation of
were mixed well with APTES solution in a suitable mass ratio APTES.39–41 Additionally, the EDS spectrum of PS@PDA/APTES
with the assistance of ultrasonication. It is known that an hybrid PC films also manifests the incorporation of APTES
APTES molecule consists of one amino group (–NH2) and three into the PS@PDA NP system (Fig. 3b). The surface chemical

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Fig. 4 SEM images of the as-prepared PC films with diverse mass ratios of
APTES to PS@PDA NPs: (a) 0 : 5, (b) 0.5 : 5, (c) 1 : 5 and (d) 2 : 5; the scale bar
is 200 mm. Inset: The magnified images of PC films; the scale bar is
500 nm. The PS core size is 186 nm.

contrast (Fig. S2b, ESI†). Besides, a number of cross-linked

APTES polymer nodules on the surface of PS@PDA NPs can be
caught in the inset image of Fig. 4c, which are consistent with
the portrayal in Fig. 2. When the mass ratio is 2 : 5, no cracks
can be observed as well (Fig. 4d); however, the structural color
Fig. 3 (a) FT-IR spectra of PS NPs (line 1, grey), PS@PDA NPs (line 2, of PCs turns to pale tea-green and the edge of PC films appears
purple) and PS@PDA/APTES hybrid PCs (line 3, blue). (b) The EDS spectrum as an distinct brown circle (Fig. S2d, ESI†), by the reason of
of PS@PDA/APTES hybrid PC films. The mass ratio of APTES to PS@PDA
superfluous APTES polymers permeating into the interstices of
NPs is 1 : 5.
PS@PDA NPs (Fig. 4d, inset). To conclude, an optimal mass
ratio of APTES to PS@PDA NPs should be about 1 : 5, with
composition of PS@PDA/APTES hybrid PCs consists of four which cracks can be absolutely removed and PC films present
elements, C, O, Si and Pt, respectively, in which the silicon brilliant structural colors.
element (2.3%, atomic percentage) is entirely ascribed to APTES SEM images of self-assembled crack-free amorphous
while Pt should be from the sputtered platinum layer on the PS@PDA/APTES hybrid PC films at various magnifications are
PS@PDA/APTES PC film before SEM observation. shown in Fig. 5a–c, where the mass ratio of APTES to PS@PDA
The amount of loaded APTES monomers strongly affects the NPs is 1 : 5. It apparently indicates that the PS@PDA NPs
performance of as-prepared PS@PDA/APTES hybrid PC films. are densely packed, out of order, revealing a crack-free and
Since the films become crackless with the increase of APTES amorphous structure of as-prepared PCs. In addition, two-
monomers, the structural color of PCs is progressively dimensional fast Fourier transform (2D FFT), executed by the
depressed, which may be attributed to the decrease of the Matlab software, has been applied to illustrate the spatial
reflective index contrast between PS@PDA NPs and the air. In information of SEM images (Fig. 5d).42 With a discretely
order to fix an optimum APTES monomer additive volume of circular ring pattern, the 2D FFT image demonstrates that the
the PS@PDA/APTES hybrid, for achieving crack-free PCs and PS@PDA/APTES hybrid PCs are isotropic and in a short-range
high color visibility simultaneously, a series of PC films were order, agreeing with the amorphous structure presented in
prepared with varied mass ratios of APTES to PS@PDA NPs. SEM images. The amorphous structure of PS@PDA/APTES
Fig. 4 and Fig. S2 (ESI†) present the SEM images and optical hybrid PCs is probably due to the bumpy surfaces of PS@PDA
photographs of these as-prepared PC films, respectively. The NPs, which are derived from the aggregation of dopamine
images clearly show that cracks in micron scale can be observed oligomers onto PS cores. And the rough surfaces of PS@PDA
(Fig. 4a) when there is no APTES blended into the building NPs would impede the ordered arrangement of particles from
blocks. As the mass ratio of APTES to PS@PDA NPs rises to crystallization, as the evaporation-induced capillary force was
0.5 : 5 (Fig. 4b), the width of cracks is apparently narrowed partially encountered by connection or friction of the bumpy
down, though miniature cracks remain in the PC films. When building particles during the self-assembly process.37 Further-
the mass ratio of APTES to PS@PDA NPs is increased to 1 : 5, more, because of Schiff base reaction/Michael addition that
cracks are absolutely excluded as demonstrated in Fig. 4c, and occurred between benzoquinone structures of the PDA shell
the structural color of PC films is tea green with high color and amino groups of APTES, the interactions among PS@PDA

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scattering across the full visible spectrum.37,43,44 Meantime, the

reflection peaks shifted to a longer wavelength (Fig. 6d and
Table S1, ESI†), from 400 nm, 454 nm and 606 nm to 448 nm,
533 nm and 652 nm, respectively. With regard to amorphous
structures, the Bragg’s law in a modified version might be
available to elucidate the transfer of wavelengths:18
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D/l p 1/n

where D is the center-to-center distance between adjacent

particles, l represents the wavelength of light and n refers to
the refractive index of colloidal spheres. On account of the
increased size of PS@PDA NPs and a higher refractive index of
PDA (B1.74) compared to PS (B1.59), the red-shift of peak
wavelengths of reflection spectra ultimately proceeded.16,45 By
further modification using APTES, the reflection peaks of
PS@PDA/APTES hybrid PC films experienced a little red-shift,
Fig. 5 (a–c) SEM images of as-prepared crack-free PS@PDA/APTES
hybrid PC films at different magnifications; the diameter of the PS core as the cross-linked APTES polymers inevitably extended the
is 186 nm. (d) The 2D FFT image of the SEM image (b). distance between PS@PDA NPs. Otherwise, the PS@PDA/APTES
hybrid PCs maintained high color visibility similar to PS@PDA
NP films (Fig. S3, ESI†), which meaningfully indicates that the
NPs were dramatically strengthened by the Si–O–Si structure of addition of APTES monomers has no detrimental influence on
cross-linked APTES polymers, which acted as a special binder. the optical performance of as-prepared PC films.46
Consequently, cracks in PS@PDA/APTES hybrid PCs can be Additionally, the PC films assembled from the PS@PDA/
widely eliminated by means of covalent bonding. APTES hybrid have wide viewing angles. By the method of direct
To investigate the optical properties of as-prepared crack- observation (Fig. S4, ESI†), the optical images of three different
free PC films, the reflection spectra of PCs fabricated from PS PC films, which are formed from the PS@PDA/APTES hybrid
NPs, PS@PDA NPs and the PS@PDA/APTES hybrid (the mass with a PS core size of 162 nm, 186 nm and 252 nm, respectively,
ratio of APTES to PS@PDA NPs is 1 : 5) in different PS/PS core display virtually identical structural colors at different viewing
sizes were measured (Fig. 6a–c), and the corresponding digital angles under ambient illumination (Fig. 7a). To comprehend
photographs can be seen in Fig. S3 (ESI†). In contrast to that more about the low angle-dependent property of as-prepared
of PS NP films, the reflection intensity of PS@PDA NP films PC films, angle-resolved reflection spectra of the blue PS@PDA/
is greatly diminished and the structural colors exhibit high APTES PC film (162 nm, PS core) were measured (Fig. 7b). The
visibility with the incorporation of the black PDA shell. It can be detection angle was varied from 01 to 601 relative to the normal
attributed to the PDA absorbing majority of incoherent light planar surface (see the detection mode in Fig. S4, ESI†).

Fig. 6 Reflectance spectra of PC films fabricated from PS NPs (blue curve), Fig. 7 (a) Photographs of crack-free PS@PDA/APTES hybrid PC films
PS@PDA NPs (green curve) and the PS@PDA/APTES hybrid (red curve); viewed from different viewing angles under ambient light; the diameters
the PS/PS core diameters are (a) 162 nm, (b) 186 nm, and (c) 252 nm. (d) The of PS cores are 162 nm (blue), 186 nm (green) and 252 nm (red); the mass
relationship between peak wavelengths (lmax) in reflection spectra and the ratio of APTES to PS@PDA NPs is 1 : 5. The scale bar is 2 cm. (b) Reflection
diameters of the PS/PS core; blue: PS NPs, green: PS@PDA NPs, red: spectra of the blue PC film at different incident angles. (c) Plots of peak
PS@PDA/APTES hybrid. wavelengths for the reflection spectra as a function of incident angle.

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which were generated from a Schiff base reaction or Michael

addition. Afterwards, PS@PDA NPs were robustly bridged by the
Si–O–Si network due to the self-condensation of APTES monomers.
In addition, benefitting from the intrinsic light absorption char-
acteristic of PDA and amorphous arrangement, the as-prepared
PS@PDA/APTES hybrid PC films exhibit high color contrast and
low angle dependency. And the demonstrated approach may be
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introduced in different colloidal sphere systems, such as poly-

methylmethacrylate (PMMA), silicon dioxide (SiO2) and titanium
Fig. 8 Hose stream tests of (a) PS@PDA film and (b) PS@PDA/APTES film dioxide (TiO2), as the mussel-inspired PDA shell is merely physically
(left: before test, right: during test); finger-wiping tests of (c) PS@PDA film adhered to the surface of colloidal particles. More importantly, the
and (d) PS@PDA/APTES film (left: before test, right: after test). The PS core robustness of PS@PDA/APTES PC films was boosted greatly due to
size is 252 nm.
the covalent bonds among building particles. We believe that this
fabrication strategy will provide an essential insight for realizing
As shown in Fig. 7c, the peak wavelengths of the blue sample crack-free amorphous PC films, which might have an ample variety
appear at almost the same position as the incident angles range of promising applications in the field of displays, such as paints,
from 01 to 601. The low angle dependence of PCs might be cosmetics, textiles and ceramics.
attributed to the isotropic nature of amorphous arrays, which
have been verified as existing in the PS@PDA/APTES hybrid PC
films as discussed before.42 Generally, the incoherent multiple Acknowledgements
light scattering contributes prominently to the entire light
We acknowledge the support by School of Chemistry and
reflection when the colloidal array is amorphous, and then
Chemical Engineering, South China University of Technology,
the color of PCs would appear white to the naked eye. Here,
for characterization.
aided by the black PDA coating on the surface of PS NPs,
PS@PDA/APTES hybrid PCs eventually demonstrated a low angle
dependent structural color with enhanced contrast. Similarly,
the full width at half maximum (FWHM) of reflectance spectra in
Notes and references
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