Professional Documents
Culture Documents
discussions, stats, and author profiles for this publication at: http://www.researchgate.net/publication/249322934
CITATIONS
READS
33
3 AUTHORS, INCLUDING:
Yiwu Mao
Jianping Ge
Tongji University
9 PUBLICATIONS 72 CITATIONS
SEE PROFILE
SEE PROFILE
Journal of
Materials Chemistry C
View Article Online
PAPER
falls within 1 s and recovers after 45 s depending on the eld strength. Since the electric eld can be
well restricted in the space between two electrodes and precisely controlled by the applied potentials, it
is possible to fabricate adjacent magnetic photonic crystal cells whose reection signals can be
DOI: 10.1039/c3tc30399c
independently controlled by the electric eld, which reveals a possible solution to high-resolution
www.rsc.org/MaterialsC
Introduction
Experimental section
2.1
Materials
Paper
were washed with ethanol 3 times and with water 2 times by
centrifugation, and nally they were dispersed in DI water to
reach a volume fraction of 8%.
2.3
A concentrated solution of PS particles was mixed with ferrouid to obtain a homogenous solution with specic PS% and
Fe3O4%. 20 mL of solution was then sealed in a glass cell
composed of two transparent and conductive ITO glasses with
an average thickness of 400 mm. The upper and bottom ITO
glasses of the unit cell were connected to the positive and
negative poles of the DC power source, respectively. The as-made
glass cell was directly used for reection measurements and
microscopic observation. The magnetic eld strength applied to
the sample was controlled by changing the distance between the
sample and a permanent magnet, or by changing the current in
electromagnets. The electric eld strength can be controlled by
setting the output voltage of the DC power source. For the
fabrication of multiple cells in one glass slide, diluted HF
solution was used to etch the ITO layer to create insulate
boundaries between 2 neighbouring cells, so that the unit cell
can be independently controlled by the DC power source.
2.4
Characterization
Table 1 Parameters for the spectroscopy measurements, including the integration time of the spectrometer, the sampling interval time, and the interval time
of electric eld switching
Fig. 1
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Integration
time (s)
Sample interval
(s)
E switching
interval (s)
0.5
0.5
0.1
0.5
0.5
0.1
0.2
4.0
1.0
0.2
5.0
4.0
Paper
applied or removed. Typically, the dispersion of monodisperse
PS colloids (3%) in ferrouid (2%) was sealed in an ITO glass
cell with an average thickness of 400 mm, which showed green
colour in a magnetic eld of 0.055 T due to the assembly of
nonmagnetic building blocks in a magnetic medium22 (Fig. 1).
The reection peak around 570 nm proved the formation of
bundle-like colloidal crystals suspended in solution. With the
magnetic eld strength unchanged, an electric potential (2.7 V)
was exerted upon the MPC, which caused the colour to turn
brown and the reection intensity to decrease immediately.
Once the electric eld was removed, they recovered in a few
seconds. However, when a relatively strong voltage (3.0 V) was
applied to the MPC, it showed the intrinsic colour of iron oxide
and the reection disappeared in just one second, both of
which would not recover even when the electric eld was
removed.
In order to understand the mechanism of switching on a
microscale level, the electrically tunable MPC was placed in an
optical microscope operated in dark-eld mode to investigate
the change of photonic structure during the electric eld tuning
(Fig. 2). When the unit cell was exposed to a magnetic eld of
0.055 T, the PS colloids with a volume fraction of 3% instantly
formed colloidal crystals in the ferrouid composed of 2%
Fe3O4 nanocrystals. As shown in the lemost image in Fig. 2,
each green dot was actually an individual microscale colloidal
crystal, and the green colour came from its 2nd order Bragg
diraction in the visible range. When a smaller electrical
potential (2.7 V) was applied to the unit cell, the micro colloidal
crystals agglomerated to form network structures, which suggested the electrostatic repulsion between the PS colloids
became weak in this case. Aer removing the electrical potential, the agglomerates immediately redispersed into the
aqueous solution as worm-like colloidal crystals. Here, the
electric eld can be considered as a sensitive stimulus, which
interferes with the colloidal crystals in solution. When the
switching is performed using a larger electrical potential (3.0 V),
the colloidal stability will be destroyed and the PS particles as
well as the Fe3O4 particles may form permanent aggregates, so
Fig. 1 (a) Scheme for electrically controlled MPCs. TEM images of (b) the Fe3O4
nanocrystals composing the ferrouid and (c) PS colloids. The scale bars are 20
and 500 nm, respectively. (d) Reection spectra of MPCs when the electric eld is
applied or removed, and (ef) corresponding photos.
Fig. 2 Optical microscope images of MPC tuned by an electric eld. The scale bar
is 10 mm. The application and removal of 2.7 and 3.0 V electrical potentials lead to
reversible and irreversible reection changes for MPC, respectively.
that the reection peaks will not be restored, even aer the
removal of the electrical eld.
The tuning of photonic structures by the electric eld was
actually caused by the change of localized ionic strength due to
the migration and redistribution of Fe3O4 nanoparticles in the
thin liquid lm. It should be emphasized again that a constant
magnetic eld is always exerted upon the sample in all experiments. Since the PS colloids and the Fe3O4 nanoparticles are
graed with highly charged carboxylate groups on the surface,
the ferrouid and the whole suspension are very stable against
aggregation, whether or not they are exposed to the magnetic
eld. The electromobilities of PS and Fe3O4 particles were
measured to be 2.685 and 3.241 mm cm V s1 respectively,
which means that the Fe3O4 nanoparticles will move faster in
the same electric eld. In the absence of electrical potential, the
external magnetic eld will induce magnetic attraction between
neighboring PS particles in the ferrouid and causes the PS
colloids to immediately assemble into colloidal crystals, which
are stabilized due to the balance between the magnetic attraction and electrostatic repulsion between PS particles. The
colloidal crystals diract green light and show up as green dots
under the optical microscope. In this case, the magnetic eld
drives Fe3O4 and PS particles to move toward the maximum and
minimum magnetic gradient respectively, so that the Fe3O4
nanoparticles tend to be enriched around the bottom ITO glass,
and the assembled PS particles are suspended near the upper
ITO glass. However, as the electrical eld was applied, some of
the Fe3O4 nanoparticles moved towards the upper ITO glass
(high potential electrode) due to their negative surface charge
and relatively large electromobility, which greatly increase the
localized ionic strength in the upper zone. The increased ionic
strength will screen the repulsion and attraction between PS
colloids, so that the assembly was disturbed, the order degree of
the colloidal crystals decreased and then the reection intensity
fell (Fig. 3). Since the diraction wavelength did not change
signicantly, the lattice spacing of the PS crystals seemed not to
change largely. Therefore, the reduction of intensity could be
attributed to the melting of colloidal crystals under the electric eld. Once the electrical potential was removed, the
magnetic nanoparticles moved back towards the bottom ITO
Paper
glass again, and the proper ionic strength for assembly was
recovered. The reason for the irreversible response to the
application of a strong electrical potential is that the negatively
charged Fe3O4 nanoparticles would be greatly neutralized and
deposited onto the upper electrode in that case, so that the
aggregation of PS colloids was unable to reassemble even
though the electrical eld was no longer applied.
The preliminary investigation into the working mechanism
of the electrically tunable MPCs implied that a good match
between the strength of the applied electrical eld and the
magnetic eld was important for the sensitivity of the reection
switch. In order to understand their relationship and to determine the optimal electric potential corresponding to a specic
magnetic eld from 0.021 to 0.06 T, the dependence of reection intensity alteration (DR) on the electric potential was
examined through a study of MPCs composed of 2% PS colloids
and 3% ferrouid. It should be noted that, with the application
and removal of electrical potential, the reection intensity
decreased and recovered accordingly, and DR here refers to
the change of reection intensity between these two states. For
example, for a specic MPC unit cell assembled by a magnetic
eld of 0.021 T, its DR rises with the increase of applied electric
potential from 2.0 to 2.3 V due to more serious melting of the
colloidal crystals (Fig. 4a). Then, DR remains the same even as
the electric potential is further enhanced to 2.5 V, which shows
that 2.3 V is an adequate strength to induce the best optical
response and it is the optimal value for MPCs at 0.021 T, since
low power consumption is always desired. Using the same
method, the appropriate electric potentials for MPCs assembled
in 0.029, 0.038, 0.048 and 0.06 T elds were determined to be
2.6, 3.0, 3.3 and 3.4 V, respectively. The strength of the working
electric eld and magnetic eld exhibited a linear relationship,
according to the simulation in Fig. 4f, which demonstrates that
a stronger electric eld is required for a MPC assembled by a
stronger magnetic eld, because a high electric potential was
essential to change the distribution of Fe3O4 NPs and thereby
the ionic strength in an enhanced magnetic eld. According to
Fig. 4f, the electrical potential for an MPC cell (2% PS + 3%
ferrouid) working under a 0.055 T magnetic eld was 3.38 V.
When the ferrouid concentration was decreased to 2%, as in
Fig. 1 and 2, the magnetic packing force exerted on the PS
colloids and the magnetic interaction between the PS colloids
became weaker, so that a lower electric potential (such as 3.0 V)
was adequate to irreversibly destroy the ordered structure.
A good match between the electric eld and magnetic eld
not only optimized the sensitivity as discussed above, but also
Fig. 4 (ae) The relationship between the optical response (DR) and the applied
electric eld for MPCs assembled by magnetic elds of 0.021, 0.029, 0.038, 0.048
and 0.06 T. (f) The optimized working electric potential increases linearly with the
increase of the strength of the applied magnetic eld.
Paper
10 periods (Fig. 5). When a weak potential (2.8 V) was exerted
upon or removed from the unit cell, the reection intensity rose
and fell accordingly with the amplitude of variation remaining
the same. However, when a strong potential (3.1 V) was selected,
the amplitude decreased sharply, although it was much larger
at the beginning of the switching. The results here were
consistent with the microscopic observations, and quantitatively
describe the inuence of an electrical eld upon the amplitude
and reversibility of the reection switching. Combined with the
linear working curve in Fig. 4f, an experimental law can be
summarized, that for a unit cell working under a specic
magnetic eld, the electrical potential falling on the simulated
straight line is an appropriate potential which leads to a good
balance between sensitivity and reversibility. A stronger electric
eld would give good sensitivity at rst, but would lead to poor
stability aer several cycles. On the other hand, for a weaker
electric eld the variation of reection intensity will be small but
the reversibility will be guaranteed. It should be noted that the
upward trend of reection signal uctuation will occur within
the rst 10 cycles for most samples, and then the alteration
reaches a plateau in the following cycles. Although we observed
the reection change going at from cycle 9 to 15 for the samples
in Fig. 4a and b, the extra cycles were not included for consistency in the recording data.
Therefore, with the electric eld nely tuned to accommodate the magnetic eld, an electrically controlled MPC-based
reection switch with reversible optical response can nally be
obtained. As shown in Fig. 6, when the electric eld (2.8 V) was
periodically applied to or removed from the photonic crystals
assembled by a constant magnetic eld (0.038 T), its reection
intensity changed accordingly over 50 continuous cycles. The
cell had been switched by an electric eld for several cycles, so
that the uctuation of reection signals is at until the end. The
interval time of the electric eld switching was set to be 4 s
according to the turn on/o time of the unit cell, which will be
discussed later. The reection signals were quite stable in each
state and the reection switching was fully reversible. It should
be noted that the change of reection intensity (DR) was larger
than that in Fig. 5a, although the material composition and
external elds were all identical, because the integration time of
Paper
devices. It is known that an external magnetic eld can be an
eective stimulus to change the optical properties of a MPC
instantly, reversibly and remotely, which makes it ideal for PC
based optical switches or display units. However, the independent control of adjacent MPC cells using a magnetic eld will be
great challenge, because it is dicult to manufacture small but
adequately strong electromagnets and avoid their eld interference, although the miniaturization of MPC cells can be
realized due to the good uidity of colloidal solutions. This
problem may be addressed by the introduction of an electric
eld, as it can be nely restricted within a small space between
two electrodes, and it can also change the optical properties of
the MPC because the building blocks are highly charged
nanoparticles. As a demonstration, we encapsulated the
colloids in three 11.5 2.5 mm cells with intervals of 5 mm,
and all of them were rst assembled into dynamic colloidal
crystals by the same large size, low strength and constant
magnetic eld beneath the glass slides. As the ITO electrodes
were insulated from each other, we could separately change the
reection intensity of each cell using a three channel DC power
source. The tuning did not interfere with the others even though
they were close to each other (Fig. 9). Certainly, the current
preliminary results may still not meet the requirements of high
resolution, but they indicate a possible solution to the problem
and open another possibility for magnetically assembled PC
systems.
Conclusions
In summary, electrically tunable photonic crystals were fabricated by encapsulating the MPCs inside an electrolytic cell, and
their reection decreased or recovered as an electric eld was
applied or removed. The switching of reection was caused by
the change of the order degree of the colloidal crystals due to
the migration of Fe3O4 nanoparticles and the alteration of
localized ionic strength with or without an electric eld. A good
match between the strengths of electric and magnetic elds was
benecial for improving the sensitivity and reversibility of
reection switching, and the working electrical potential linearly increased with the increase of magnetic eld strength. The
turn on speed of the reection switch is determined by
the magnetic eld, while the turn o speed is determined by the
electric eld. Since the electric eld can be well restricted in
the space between two electrodes and precisely controlled by the
applied potentials, we were able to fabricate adjacent MPC cells
whose reection signals can be independently controlled by
the electric eld, which may have potential applications in
MPC-based optical devices.
Acknowledgements
J. Ge thanks the support from National Science Foundation of
China (21001083, 21222107), Shanghai Pujiang Program
(10PJ1409800), Shanghai Rising-Star Program (13QA1401400)
and the Scientic Research Foundation (SRF) for the Returned
Overseas Chines Scholars (ROCS), State Education Ministry
(SEM).
Paper