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Simple and Ultrafast Fabrication of Invisible Photonic

Prints with Reconfigurable Patterns
Yang Hu, Dongpeng Yang,* and Shaoming Huang*

tunable particle sizes can be synthesized

Photonic prints integrated with invisible and reconfigurable patterns are in large-scale and low cost, which can
highly desired due to their potential applications in combining anti-counter- be packed into ordered structures with
feiting, anti-photobleaching, and low-resource consuming. Here, a simple good quality. By introducing responsive
building blocks, polymers, or other com-
and fast approach is reported to fabricate invisible photonic prints, which are ponents into the colloidal photonic crys-
prepared by coating a layer of oleylamine (OAm) on the selective region of tals, responsive photonic crystals can be
hydrophilic photonic paper. Owing to the different wettability and swelling prepared and their color can be changed
ability between the pattern and background regions, the pattern of the as- depending on the physical or chemical
prepared sample is invisible (Δλ = 0) at normal conditions, while it can be stimulations.[3–5] These photonic crys-
tals with brilliant structural colors have
revealed with a large color contrast (Δλ = 140 nm) in the presence of water
attracted considerable interests due to
with a very short time (≈2 s). The hiding–showing transition is fully reversible their growing applications in the field of
and the sample shows good performance in long lasting stability. With elabo- reflection mode-based color display,[6–11]
rate mask, the presented method is also capable of preparing microscopic sensor,[12–20] printing,[21–27] anti-counter-
invisible photonic print with high resolution. Moreover, the pattern of the feiting,[28–34] optical device,[35–39] photoca-
invisible photonic print can be reconfigured repeatedly through the erasing talysis,[40–43] and solar cell.[44–46]
Photonic crystal prints show intrinsic
and reconstructing process, which works well in macro/microscopic scale. advantages in color display and infor-
The combination of invisible and reconfigurable properties as well as the mation storage due to their structures
invisible photonic prints with macro and microscopic patterns will facilitate induced anti-photobleaching properties
their practical applications such as anti-counterfeiting, message storage, and compared to the conventional organic
display. dyes or heavy metal pigments. The tradi-
tional photonic prints with tailored color
contrast between the pattern and back-
ground have been widely investigated.
1. Introduction These visible photonic prints with elaborate patterns can be
prepared through ink-jet printing of particles with different
Photonic crystals are originated from the interactions between sizes,[26] and selective fixing the structures of photonic crystals
the periodic micro/nanostructures and the visible light, by UV light,[47,48] magnetic,[49] and electric field.[7,21,50] In con-
resulting in a photonic bandgap (PBG) that prevents a cer- trast to the visible pattern, invisible photonic prints that can
tain wavelength from penetration of the ordered structures. hide and show the patterns under normal circumstance and
This will lead to the selective reflection of light, thereby bril- external stimulus respectively are appealing especially in coun-
liant colors that can be observed by naked eyes, which is called terfeiting of high security. However, the practical applications
structural color.[1,2] The reflection peak and structural color can of invisible photonic prints remain a big challenge due to the
be altered by controlling the structure constant or the refrac- following ­reasons: 1) the contrast of the reflection peak between
tive index of photonic crystals. Among the various kinds of the pattern and background must be as small as possible (ideal
photonic crystals, colloidal photonic crystals have been widely state: Δλ = 0) in order to hide the pattern into the background
investigated because monodispersed colloidal particles with at normal conditions, 2) the color contrast between the pat-
tern and background should be as large as possible to reveal
the pattern when the external stimulation is applied, 3) the
Y. Hu, Dr. D. P. Yang, Prof. S. M. Huang
School of Materials and Energy
invisible pattern can be reconfigured repeatedly to realize the
Guangzhou Key Laboratory of Low-Dimensional Materials low resource consuming and environmentally friendly mate-
and Energy Storage Devices rials, and 4) the whole fabrication and reconfiguration process
Guangdong University of Technology should be simple, fast and efficient in an economic way.
Guangzhou 510006, P. R. China Currently, various strategies have been developed to fab-
E-mail: dpyang@gdut.edu.cn; smhuang@gdut.edu.cn
ricate invisible photonic prints on the basis of cross-linking,
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adom.201901541.
drying, or modification of the selected regions of photonic
papers, and the patterns can be revealed by dint of water,[51–54]
DOI: 10.1002/adom.201901541 deformation,[55,56] magnetic field,[57] UV light,[58] and vapor of

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s­ olvents,[59] ­
respectively. Most of the fabrication approaches
need time-consuming or complex fabrication processes to
guarantee the success hiding and showing the pattern in the
absence and presence of external stimulus, respectively. Cross-
linking route is widely used for creating invisible patterns
by fixing the selective region of the photonic paper with the
help of cross-linkers, leading to a color contrast (60–80 nm)
between pattern and background when water or deformation is
applied.[41,55,56] However, the introduction of cross-linkers into
photonic crystals will inevitably alter the structures or refrac-
tive index of pattern region, thereby inducing a reflection peak
contrast about 10–15 nm, which is unfavorable for hiding the
patterns. For magnetic gel,[57] the long-lasting stability will be
a problem as the solvents in the gel will evaporate over time,
resulting in the failure of revealing the pattern. Selective
etching[59] is promising in fabricating invisible photonic prints,
whose pattern can be fully hidden since there is no color
contrast between the pattern and background. Nevertheless, it
seems to be a big challenge in printing the patterns with high
resolution. More importantly, due to the permanent change of
structures of the photonic crystals, none of the pattern can be
reconfigured using the aforementioned strategies. Therefore,
developing an effective method to deal with the above problems
is highly desired.
In this work, we present a simple and ultrafast method to
fabricate invisible photonic prints with reconfigurable pat-
terns by selective coating oleylamine (OAm) on the hydrophilic
photonic paper. The key to our approach is to create the dif-
ferent wettability between the pattern (coated) and background
(uncoated) region through selective coating. The pattern of the
fabricated invisible photonic print can be revealed and hidden
in the presence of water and dried state, respectively. The
showing-hiding process is fully reversible and the as-prepared
sample show long lasting stability without losing its resolution.
Microscopic invisible photonic with good performance also can
be fabricated with mask of fine resolution. In addition, due the
noncovalent absorption of OAm on the photonic paper, the
invisible pattern can be reconfigured by erasing the original
pattern and reconstructing a new pattern through the selective
coating strategy. The reconfigurable process can be repeated
for many times and can be realized in macro and microscopic
scale. The current invisible and reconfigurable printing method
together with invisible patterns will make the practical utiliza-
tions of invisible photonic prints possible in anti-counterfeiting
and security.
2. Results and Discussion
The fabrication of invisible photonic prints with reconfigurable
patterns can be accomplished by 1) the preparation of water
responsive photonic paper, 2) printing invisible pattern on the
hydrophilic photonic paper through selective coating OAm on
the pattern region, and 3) reconfiguring the pattern via erasing
the premade pattern and subsequently reconstructing a new
desired pattern. Typically, the water responsive photonic paper
was prepared by the self-assembly of monodispersed silica
particles into polymerizable oligomer (poly(ethylene glycol)
methacrylate, PEGMA) to form metastable colloidal crystals,
Adv. Optical Mater. 2020, 1901541 1901541 (2 of 10)
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which was then fixed by photopolymerization. The as-prepared
photonic paper shows a narrow stop band located at 475 nm
(Figure 1a) with corresponding blue color (Figure 1b). The
strong reflection intensity and brilliant structural color indicate
the highly ordered structures of the photonic paper, which can
be evidenced by the plenty of bright blue dots from the cor-
responding microscope image (Figure 1c) and the ­crystalline
structures (Figure 1d,e) from the scan electron microscope
(SEM) images. Under SEM, most of the silica particles are
packed into long-range ordered structures with (111) facet
exposed. These silica particles are nonclosed packed because
silica particles have a much lower volume percentage (35%)
than that of close packed photonic crystals (74%), thereby
PEGMA are infilled into the gaps between particles. Similar to
the traditional photonic crystals, the structural colors of the poly­
meric photonic paper can be precisely controlled with particles
of different size. When silica particles with average diameter
of 190, 200, and 221 nm are used, photonic papers with bright
green, yellow, and red colors and reflection peaks located at 540,
600, and 657 nm can be achieved (Figure 1a,b), respectively.
These responsive photonic papers can be swelled by absorption
of water molecules into the polymeric matrix, thus, changing
their lattice constants and structural colors. It should be men-
tioned that the swelling ability of the photonic paper is mainly
determined by the fraction of the hydrophilic polymer. In this
regard, the high percentage of PEGMA (65%) of the photonic
paper will favor the fast swelling of the photonic paper and the
rapid showing of the invisible pattern in water correspondingly.
For invisible photonic prints, the efficiency of fabrication
and the performance of invisible photonic prints are extremely
crucial to realize their practical applications. Briefly, invisible
patterns with good hiding–showing performance, excellent
­
reversibility, fast showing speed, fine resolution, outstanding
reconfigurability, and long-lasting stability are necessary. In this
work, the as-prepared invisible photonic prints can fulfill all the
above requirements that can be fabricated in a facile and effi-
cient way.
The blue photonic paper (Figure 2a) was used for the proof
of the concept to show the fabrication of invisible photonic
prints. The pristine photonic paper shows bright blue under
the illumination of ambient light, which possesses a reflec-
tion wavelength at 470 nm (Figure 2d). The adhesive mask
with circular pattern was covered onto the photonic paper to
protect the hydrophilic region from further modification. Then,
excess OAm were covered on the bare region (Figure 2b, coated
region) in order to alter the wettability and hinder the swelling
ability of the OAm coated region in water. After OAm coating,
the structural color and reflection peak remain unchanged,
indicating the uncoated and coated regions have the similar
structures. This can be explained by that the transparent OAm
molecules are majorly absorbed on the surface of the photonic
paper, which will not change neither the lattice constant nor
refractive index of photonic paper. The absorption of OAm on
the surface of photonic paper can be identified by the Fourier
transform infrared spectrum (FTIR, Figure 2e). Compared to
the uncoated region, the coated region exhibits two additional
peaks (blue arrows) due to the absorption of OAm molecules.
The absorption located at 3325 cm−1 can be attributed to the
absorption of NH bond, while the peak around at 2922 cm−1
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Figure 1. a) Reflectance spectra, b) digital photos, c) microscope images of photonic papers with blue, green, yellow, and red colors. d,e) SEM images
of photonic paper with blue structural colors.
can be assigned to the CH bond, proving the presence of OAm
on the surface of photonic paper. In addition, the SEM image
(Figure 2f) and corresponding mapping scan results (Figure 2g)
of the coating region prove the elements N from the OAm are
concentrated on the top layer and top of the cross-section. The
thickness of OAm along the cross-section is determined to be
about 1.5 µm. Finally, the photonic print with invisible circular
pattern was obtained after peeling off the mask.
The pattern of the invisible photonic print can be shown by
addition of water (Figure 2c), firmly demonstrating the suc-
cess fabrication of the invisible pattern using the presented
method. The pattern can be recognized in seconds and stabi-
lized in excessive water at least for 40 s. Further prolonging the
immersing time will induce the swelling of the pattern region
by the excessive water (Figure S1, Supporting Information),
leading to a blurry pattern. However, after drying, the pattern
can be hidden back and show itself again in water.
Compared to the previous approaches, the presented
methods for preparing invisible photonic prints have fol-
lowing advantages: 1) The presented fabrication is rather
simple, efficient, and straightforward since all the materials
are commercially available and no special operations or equip-
ment are needed. 2) The fabrication of invisible pattern can
be accomplished with a very short time, and any desired
pattern can be constructed on the photonic paper with only
30 s, which is much faster than that of conventional
approaches (>30 min). 3) The invisible pattern can be recon-
figured in a simple, convenient, and efficient way, which will
be shown latter.
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The strong absorption of OAm onto the photonic paper is
the key to create invisible pattern. The hydrogen bond between
the amidogen groups from the OAm and the hydroxyl groups
from PEGMA is supposed to be the major interaction that
­contributes to the strong absorption. In order to verify this,
1-octadecene (ODE) and oleic acid (OA) with similar chain
length but different functional groups are used to replace the
OAm to fabricate invisible photonic prints. The results are illus-
trated in Figure S2 in the Supporting Information. According to
the color change of the prints in water, both of the ODE and OA
are failure in preparation of invisible patterns. In principle, it
is hard to form hydrogen bond between the ODE and PEGMA
due to the lack of functional groups in ODE. For OA, it seems
to be possible that hydrogen would form between the OA and
polymer. However, the intermolecular hydrogen bond between
the organic acid so strong that the organic acid prefers to form
dimer with another organic acid rather than the formation
of hydrogen bond with other molecules. Therefore, invisible
pattern cannot be constructed owing to the weak absorption
capacity of OA. These results suggest that the hydrogen bond
is the driving force for the good adsorption of OAm on the
photonic paper.
Owing to the selective coating, the uncoated and coated
regions show different swelling ability in water, giving rise to
the showing of patterns (Figure 2c) with a large color contrast
in seconds once the invisible photonic print is immersed into
water. Here, in order to compare the different swelling ability
between the uncoated and coated regions, 3D color filled contour
map is used to collecting the reflection variations as function of
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Figure 2. a–c) Construction of invisible pattern which can be shown in water, d) reflectance and e) FTIR spectra of the uncoated and coated region.
f) SEM image and g) corresponding N mapping of the cross-section of the photonic paper coated with OAm.

the time. The reflection peak of uncoated region shifts from
466 to 610 nm in water with seconds (Figure 3a) while the cor-
responding wavelength of coated region only red shift less than
5 nm even for a long time (Figure 3b). Thus, a large contrast of
reflection peaks Δλ = 140 nm can be obtained, which is much
larger than that of most conventional results (<100 nm). It is
known that the hydrophilic function groups give high wet-
ting property with low contact angle. Without the coating, the
polarity of hydroxyl groups and PEG chains of PEGMA con-
tribute to the hydrophilic property to water molecules, hence,
the uncoated photonic paper has a low contact angle of 11°
(Figure 3c). The absorption of water into the polymer matrix
will make the polymer expanded, leading to an enlarged inter-
particle distance (Figure 3e) and causing a large variation of
structural colors. In contrast, the region coated with a homog-
enous OAm layer exhibits a weak hydrophilic property with
a high contact angle of 64° (Figure 3d) due to the existing
CH3(CH2)7CHCH(CH2)7CH2 groups. These hydrophobic
groups are supposed to be terminated on the photonic paper
to prevent the hydrophilic polymer from absorbing water
molecules. Therefore, the lattice constant, (Figure 3f) the wave-
length, and reflection intensity (Figure 3b) of coated region
show negligible change. It should be noted that the color con-
trast between the pattern and background can be well adjusted
by altering the amount of water, as illustrated in Figure S3 in
the Supporting Information. Through careful addition of water
with 6 and 3 µL, the photonic print with blue-red and blue-
green color contrast can be obtained, respectively.
In addition to the peak shift, both the intensity and the
bandgap of reflection peak of uncoated region gradually
increased, which helps to reveal the pattern with high color
saturation. Actually, although the peak intensity reaches the
highest point in ≈10 s, the peak shift of uncoated region was
finished in ≈2 s, indicating the fast showing speed of the pat-
tern. It is known the bandgap widens considerably as the dielec-
tric contrast is increased, which is equivalent to a large ­contrast

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Figure 3. a,b) Reflection spectra, c,d) water contact angle, and e,f) SEM images of a,c,e) uncoated region and b,d,f) coated region in the presence of
water.

of refractive index. The refractive index of SiO2, PEGMA, and
water is 1.460, 1.464, and 1.300, respectively. Therefore, the pat-
tern region of photonic paper will have a large dielectric con-
trast compared to that pristine one, which enhances the light
scattering at the interface of two dielectric materials so that
more saturated structural colors can be produced in water.
Hence, a large color contrast, enhanced color saturation, and
fast showing speed can be accomplished when revealing the
invisible pattern.
After water is removed from the photonic paper, the pat-
tern returns back to the invisible state (Figure 2b), and the
hiding–revealing transition is fully reversible. When the wetted
photonic paper is dried, the polymer will shrink. Correspond-
ingly, the lattice constant, reflection peaks, and the structural
color of the uncoated region will recover back to the invisible
state. Hence, the pattern cannot be identified, and the entire
photonic paper shows uniform blue similar to the pristine
appearance. Figure 4a represents the reflection peak shift
of the uncoated and coated regions in water and dried state,
respectively of the invisible photonic prints. The peaks merge
at invisible state, while a large contrast of reflection wavelength
can be achieved in the presence of water. The hiding–showing
switch is fully reversible and works well at least for 100 cycles
and even more. In addition, the print can interchange the invis-
ible and visible state for many times (Figure 4b) without losing
the resolution of the pattern because of the strong absorption of
OAm on the surfaces of the photonic paper.
Except for the macroscopic patterns, invisible prints with
high-resolution pattern also can be fabricated using elabo-
rate mask. A mask containing circular arrays with average

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Figure 5. a) Invisible photonic print with various patterns. b) Swellable

circulars and c) un-swellable circular arrays shown in water. d) Swellable
curved lines.

Figure 4. a) Changes of the reflection peaks of the uncoated and coated

regions in water and dried state. b) Digital photos of the invisible photonic (Figure 6c). Since the OAm molecules are physically absorbed
print in the continuous hiding and showing process. on the photonic paper, the hydrophobic pattern can be erased
by solvents that can dissolve OAm molecules, such as alcohols
­ iameter of 150 µm is used to print invisible photonic pattern
d and most nonpolar solvents. Here, ethanol is used as eraser
in microscale. The gaps were coated with OAm ­ selectively, due to its good solubility of OAm, low cost, medium evapora-
while the circular arrays were kept as it is. As expected, the tion speed, and environmentally friendly properties. When the
circular array and gaps possess similar structural colors invisible photonic print was immersed into the ethanol, with
(Figure 5a) in the beginning, proving the invisible state. When only ≈15 s, the premade pattern of invisible photonic print was
the print is immersed into water, the structural colors of the totally erased (Figure 6a) due to the OAm was completely dis-
uncoated arrays turn green immediately (Figure 5b) owing to solved in ethanol. The OAm coated region turns from hydro-
the swelling effect, while the gaps remain blue because of the phobic to the hydrophilic, which can be confirmed by the low
weak hydrophilic surfaces. The resolution of circular is about water contact angle and large shift of its reflection peak in water
165 µm, and it is supposed to be much higher when a mask whose tendency is similar to the uncoated region (Figure S4,
with higher resolution is used. Similar to the macrosize pat- Supporting Information). The reconstructing of new pattern is
tern, for the micropattern, the color contrast between the pat- accomplished by the same procedures through repeating the
tern and the background also can be altered based on the water
amount (Figure 5c), while the pattern can be well controlled
with different mask (Figure 5d). Once the water is evaporated,
the color of the circular returns back to the invisible state,
and the hiding–showing process is fully reversible. Therefore,
with the help of micromasks, the invisible photonic prints with
high-resolution patterns and good performance can be achieved
using the selective coating approach.
Due to the noncovalent link of OAm on the photonic paper,
the invisible pattern can be reconfigured repeatedly in a fast
and facile way. The reconfigurable printing processes include
the erasing of premade pattern and reconstructing a desired
pattern with a new mask. To demonstrate this, photonic print
with an invisible bear pattern was prepared through the selec-
tive coating a bear on the blank photonic paper (Figure 6a).
As expected, the photonic print is invisible at dried state Figure 6. Reconfigurable construction of invisible photonic pattern. The
(Figure 6b), which can be identified in the presence of water diameter of the circular is 1 cm.

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aforementioned selective coating approaches. The same bear
pattern is reconstructed on the erased photonic paper with the
coating and uncoated region inversed compared to the original
one. As illustrated in Figure 6d,e, the new bear pattern is invis-
ible at normal condition, which was revealed with a red pattern
and blue background in water with seconds. Furthermore, the
reconfigurable process also can be realized in microscopic scale
(Figure S5, Supporting Information) in a short time, indicating
the versatile advantages of present printing method. These
results vividly demonstrate the macro/micropattern of invisible
photonic print can be precisely reconfigured by the erasing–
reconstructing process with high efficiency.
In order to evaluate the reconfigurable count of the pattern,
a blank photonic paper was prepared, which was alternant
coated with OAm and erased by ethanol. 3D color map is used
to record its water swelling ability of the coated and erased
state, thus determining whether the pattern can be reconfig-
ured repeatedly through continuous erasing and reprinting pro-
cess. One complete reconfigurability must be the combination
of erasing and subsequently reconstructing process. The peak
of the photonic paper shifts a little once the OAm are coated,
while a large peak shift similar to the uncoated can be observed
after erasing (Figure 7a). In the continuous reconfigurable pro-
cess, the periodical shift of the peaks of the coated and erasing
state can be observed, which proves the pattern can be recon-
figured at least for 20 times and even more. In addition, the
invisible patterns with 20 different patterns was through the
reconfigurable process on one photonic paper are presented in

Figure 7. a) The water responsibility of the photonic paper through continuous alternant coating and erasing process. b) Digital photos of the invisible
photonic print with reconfigurable patterns that can be hidden and shown at dried state and in water, respectively. The diameter of the circular is 1 cm.

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Figure 8. a) Variation of the reflection peaks of the invisible photonic prints at dried state and different relative humidity (RH). The U and C represent
the uncoated and coated region, respectively. b) Digital photos of the invisible patterns stored in various RH and then wetted by water.
Figure 7b. In the beginning, all the patterns cannot be recog-
nized at dried state. On the contrary, in the presence of water,
the background of the invisible photonic prints changes its
color to red quickly, whereas the patterns still show blue color,
producing a large color contrast and consequently revealing
the pattern. Moreover, all the patterns have clear shapes and
distinct edges, implying each reconfigurable process is inde-
pendent to the others without losing its resolution. After water
evaporation, the patterns recover back to its invisible state, and
the hiding–showing switch is always reversible for each pattern.
It should be mentioned that any desired pattern can be recon-
figured in a very short time (≈45 s) and with easy operations,
proving the superiority of presented method in fast reconfig-
uring pattern.
The moisture has negligible effect on the stability of the
hidden patterns. As shown in Figure 8, the peak of the invis-
ible photonic print shifts to a longer wavelength as the relative
humidity (RH) increased. Interestingly, the pattern and the
background show similar reflection peaks, indicating the pat-
tern can be hidden in various RH. The slow absorption speed
of water molecules from the air with various RH will cause the
homogeneous swelling of the pattern and background, contrib-
uting to the hiding of the patterns. After immersing in water,
all these patterns can be well identified with a large contrast.
These results demonstrate the as-prepared invisible photonic
prints are applicable under various RH.
The invisible photonic prints show the long-lasting sta-
bility, which is rather important for the practical utility. As a
demonstration, an invisible photonic print with a half area
coated with OAm is printed. The pattern of the photonic
print is invisible at normal condition. After being stored for
0–40 days, the pattern is still invisible as can be verified by
the same peak position of the coated and uncoated regions at
dried state, while it can be shown with the large color contrast
in the presence of water (Figure 9a). Additionally, the long-
lasting stability and the good performance of the invisible
photonic pattern can be further revealed by the different color
variations between the coated and uncoated region. Similar
to the spectral results, the pattern is always invisible at dried
state after stored for a long time. When it is entrapped in
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water, the pattern with half blue and red is revealed in water
with seconds (Figure 9b). Once the water is evaporated, the
color contrast disappears and the photonic print changes back
to the invisible state. The hiding–showing switching is fully
reversible for different day. Moreover, the pattern of the invis-
ible photonic print still can be reconfigured repeatedly with
a short time (≈45 s) after being kept for more than 40 days
(Figure 9c). This outstanding stability combing the reconfig-
urability makes the practical usage of invisible photonic prints
possible in our daily life particularly in structural color related
anti-counterfeiting.
3. Conclusion
In summary, invisible photonic prints with reconfigurable pat-
terns are fabricated by coating OAm on the selective region of
the hydrophilic photonic paper, which can be revealed in water
instantly. The fabrication process is simple, fast, convenient,
and efficient, and any desired pattern can be constructed in
≈30 s. The pattern is fully invisible with Δλ = 0 at dried state,
while a large color contrast with Δλ = 140 nm is obtained
once the invisible photonic pattern is immersed in water. The
­pattern can be distinguished in water with ≈2 s and returns
back to the invisible state after the water is evaporated, and the
hiding–showing interchange is fully reversible. Also, the cur-
rent printing method can be used to prepare invisible photonic
micropattern with high resolution and good performance. Fur-
thermore, the invisible pattern can be reconfigured through
erasing the premade pattern and subsequently reconstructing
a designed pattern on the photonic paper. The reconfigur-
able process can be accomplished in very short time (≈45 s)
with easy operations and can be repeated many times. More-
over, the invisible photonic print exhibits good stabilities for
a long time and is applicable under various relative humidity.
The simple and ultrafast fabrication, as well as the reconfigur-
able patterns, the good hiding–showing reversibility, the fast
revealing speed, and the outstanding stability of the invisible
photonic print will facilitate the practical applications in the
fields of anti-­counterfeiting and message storage.
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Figure 9. a) Reflection variation, b) digital photos of the invisible pattern in the absence/presence of water after being stored for 0–40 days. c) Photos
of the original pattern that is reconfigured repeatedly after stored for 40 days. The diameter of the circle is 1 cm.

4. Experimental Section
Materials: Tetraethyl orthosilicate (98%), ethanol (EtOH, 99%), and
aqueous ammonia (28%) were purchased from Sinopharm Chemical
Reagent Co. Ltd. Poly(ethylene glycol) methacrylate (PEGMA, Mn:
360), trimethylolpropane ethoxylate triacrylate (ETPTA, Mn: 428) and
oleylamine (70%) were obtained from Sigma-Aldrich. All the chemicals
were used as received without further purifications.
Preparation of Photonic Crystal Paper: The photonic crystal paper was
fabricated according to the previous report. Monodispersed silica particles
with diameter ranging from 100 to 300 nm were prepared by the well-
known Stöber method. Then silica particles (0.035 mL) were dispersed
in the mixture of ethanol (1.1 mL) and PEGMA (0.065 mL) containing
5 vol% 2,2-dimethoxy-2-phenylacetophenone (DMPA, 99%). The mixture
was heated in oven at 90 °C for 2 h, and a concentrated pre-assembly
solution with volume about 0.1 mL was obtained. Briefly, 0.015 mL of the
pre-assembly solution was sandwiched between two glass slides with an
interval of 0.09 mm. After being exposed to UV (365 nm, 4.8 mW cm−2)
light for 3 min, the liquid film was converted to solid film with brilliant
structural colors. One side of the photonic crystal film was fixed on a piece
of glass with the help of PETPTA in order to facilitate the printing process.
Reconfigurable Printing of Invisible Photonic Prints: Typically, an
adhesive mask with designed groove pattern was covered onto the
premade photonic paper, and then OAm was covered on the pattern
region. After standing for 30 s, the excess OAm was removed by lens
paper. Finally, the mask was removed and invisible photonic pattern
could be obtained at normal conditions, which showed color contrast
when the patterned photonic paper was immersed in water. To
reconfigure the pattern, the invisible photonic pattern could be erased
as the photonic paper was immersed into ethanol for 10 s. After being
dried in oven, the photonic paper could be reprinted with mask of
different patterns.
Characterization: The assembly structures of APCs were investigated
by the HITACHI SEM-SU8010. FTIR spectra were obtained on a
Thermofisher Nicolet IS50 FTIR spectrometer ranging from 4000 to
400 cm−1. The optical microscope images and microscopic reflectance
spectra were obtained on an Olympus BXFM reflection-type microscope
operated in dark-field mode. The reflectance and backscattering
spectra at different angles were measured by a NOVA spectrometer
(Hamamatsu, S7031). The RH of 11%, 33%, 54%, 75%, 85%, 97% could
be provided as saturated solutions of LiCl, MgCl2, Mg(NO3)2, NaCl, KCl,
or K2SO4 stored in a closed chamber. Typically, a petri dish 90 mm in
diameter and 15 mm in height was filled with 50 mL saturated solution,
which created a humidity chamber of 45 cm3 above the solution. The
photonic crystal film was placed inside the chamber for 2 h, and the
corresponding reflection spectra were recorded.

Adv. Optical Mater. 2020, 1901541 1901541 (9 of 10) © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (51420105002, 51920105004, and 51672193) and
the General Program of Natural Science Foundation of Guangdong
Province (501190134).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
counterfeiting, invisible patterns, photonic crystals, photonic prints,
reconfigurable patterns, simple fabrication
Received: September 12, 2019
Revised: December 10, 2019
Published online:
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