NIR light-directing self-organized 3D photonic superstructures loaded with anisotropic plasmonic hybrid nanorods

Article abstract of DOI:10.1039/c5cc06146f

Self-organized 3D photonic superstructures loaded with plasmonic hybrid nanorods were found to undergo structural transformation from body-centered cubic to simple cubic upon NIR-light irradiation resulting from the "photothermal effect" of gold nanorods.

Full text of DOI:10.1039/c5cc06146f

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Li, Chem. Commun., 2015, DOI: 10.1039/C5CC06146F.
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DOI: 10.1039/C5CC06146F
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NIR Light-Directing Self-Organized 3D Photonic Superstructures
Loaded with Anisotropic Plasmonic Hybrid Nanorods †
Received 00th January 20xx,
Accepted 00th January 20xx
Ling Wang a‡, Karla G. Gutierrez-Cuevas a‡, Hari Krishna Bisoyi a, Jie Xiang a, Gautam Singh b, Rafael
S. Zola c, Satyendra Kumar b, Oleg D. Lavrentovich a, Augustine Urbas d, and Quan Li a*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Self-organized 3D photonic superstructures loaded with plasmonic nanostructures. Importantly, being “soft” makes them
hybrid nanorods were found to undergo structrual responsive to various stimuli, resulting in the tunability of
transformations from body-centered cubic to simple cubic upon photonic band gaps that holds immense potential for use in
NIR-light irradiation resulting from the “photothermal effect” of all-optical
integrated
circuits
and
next-generation
nanorods. Furthermore, dynamic NIR light-directed red, green and communication systems.4 Among various external stimuli such
blue reflections of the nanocomposites were demonstrated.
as electric field, magnetic field, temperature and chemical
reactions, light stimulus is particularly fascinating because of
its remote, spatial, and temporal controllability in different
environments.5 Recently, we have demonstrated reversible
manipulation of the photonic band gap in photoresponsive BP
nanostructures under the UV or visible light irradiation and
achieved dynamic optical-tuning of the reflected color across
the visible spectrum.2a Unfortunately, the use of high-energy
UV light in these systems might result in materials damage,
photochemical contamination, and poor penetration through
the container walls. Utilizing near infrared (NIR) light would be
much preferred in areas of life sciences, materials science, and
aerospace applications owing to its invisibility and superior
penetration for remote activation.6 Therefore, there are
multitude incentives to explore the novel strategy to develop
materials systems with NIR-light-responsive properties and
functions.
Recently, plasmonic gold nanorods (GNRs) are attracting
increasing attentions especially in biomedical applications due
to their appealing “photothermal effect”, converting NIR light
into heat through a non-radiative relaxation process of
longitudinal surface plasmon resonances (LSPR).7 It is also
noteworthy in this context that the characteristic wavelength
of the LSPR signal corresponding to NIR absorption can be
expediently tuned on demand by suitably altering the aspect
ratio of GNRs,8 and GNRs have been proposed for use in a few
triggering systems where UV or visible light are not favorable.9
However, adequate and homogeneous dispersion of
conventional GNRs into complex LC medium with self-
organized 3D photonic superstructures has always been a
challenging task due to their bad miscibility in LCs and
destabilization of the 3D lattices. Herein, we have judiciously
designed and synthesized new mesogen-functionalized
anisotropic plasmonic GNRs (M-GNRs), and incorporated them
Endowing remote and dynamic controllability to self-organized
three-dimensional (3D) photonic nanostructures with tunable
functionality is a principal driving force in the bottom-up
nanofabrication of intelligent stimuli-responsive materials and
devices.1 Liquid crystalline blue phases (BPs) capable of self-
organizing into periodic cubic superstructures undoubtedly
represent such an appealing functional system due to their
unique photonic band gap with selective reflection of incident
light and the consequent potential for device applications.2
BPs are among the most attractive self-organized liquid crystal
(LC) superstructures, which exist between the isotropic phase
and cholesteric phase in highly chiral nematic LCs and
generally over a very narrow range of temperature. Depending
on the temperature and chirality, the LC molecules usually
tend to self-organize into two distinct periodic 3D
nanostructures with body-centered or simple cubic symmetry,
called blue phase I (BP I) or blue phase II (BP II), respectively.3
In contrast to the conventional photonic crystals fabricated via
expensive and scale-prohibitive manufacturing, the inherent
self-organization of these soft materials makes them quite
advantageous for cost-effective production of 3D periodic
a.Liquid Crystal Institute and Chemical Physics Interdisciplinary Program, Kent State
University, Kent, Ohio 44242, United States. *E-mail: qli1@kent.edu; Tel: +1-330-
6721537
b.Department of Physics, Kent State University, Kent, Ohio 44242, United States.
c. Departamento de Física, Universidade Tecnológica Federal do Paraná-
Apucarana, PR, 86812-460, Brazil
d.Materials and Manufacturing Directorate, Air Force research Laboratory,
WPAFB, Dayton, Ohio 45433, United States
.
.
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
‡ These authors contributed equally to this research.
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into a BP LC medium composed of commercially available nm was observed at 40.7 oC. When doped with M-GNRs at
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components. Because of the optimized mesogenic concentrations ranging from 0.03 wt% toD0O.0I:710w.10t%39/(CFi5gCuCr0e6124b6)F,
functionalization, the resulting M-GNRs can be homogeneously the mixtures showed an increasing BP I temperature range
o
dispersed in the LC medium. Interestingly, the resultant GNRs- with a maximum width of 6.9 C. Further addition of the GNRs
impregnated 3D photonic superstructure was found to be suppressed the range, whereas the BP II temperature range is
stable and undergo structural transformations from body- almost independent of M-GNRs’ concentration. It was also
centered cubic to simple cubic symmetry upon the irradiation observed that the maximum reflection wavelength of BPs red-
of a NIR laser, resulting from the “photothermal effect” of M- shifted to ~650 nm when doping with 0.07 wt% M-GNRs,
GNRs, whereas its reverse process takes place upon removal of which may be attributed to the increase in the unit cell lattice
the laser irradiation. Furthermore, dynamic NIR light-directed constant of BPs.
red, green and blue reflections of the light-driven 3D photonic
(a)
(b)
nanocomposites have been demonstrated. To the best of our
knowledge, reversible or irreversible NIR-light directed
transitions of 3D photonic superstructures have not been
reported so far.
(a)
(b)
Figure 2. (a) Reflection wavelengths of the newly developed BP
medium as a function of temperature; (b) Effect of the concentration
of M-GNRs on the temperature range of BPs.
5
[Iso. 140C SmB 80C Cr.]
As is well known, the narrow temperature range of BPs is
caused by their frustrated structure, in which the regions of
double twist tile space through lattice of disclinations; the high
energy cost of the disclination cores with reduced
orientational order makes the BPs stable only in the vicinity of
the isotropic melt.3 This is why one of the approaches to
expand the temperature range of the BPs is based on
attracting foreign particles such as polymers to the disclination
core that replace the costly misaligned LC regions.12 Extensive
studies have indicated that not only polymers but also metal
and inorganic nanomaterials may act in a similar fashion to
reduce the energy cost of the disclination cores and hence
enhance the stability of BPs.13 Herein, a possible mechanism
CTAB-GNRs
Hydrophobic plasmonic M-GNRs
Figure 1. (a) Schematic representation on new mesomorphic
surfactant grafted on the GNR by covalent Au-S linkage to form
5
hydrophobic anisotropic plasmonic M-GNRs; (b) UV-vis-near-IR spectra
of CTAB-GNRs dispersed in an aqueous solution and M-GNRs in the
chloroform solution. The inset shows the TEM image of M-GNRs.
The new LC surfactant
5 was prepared by a straightforward
1
synthesis, its chemical structure was well-identified by H and
13C NMR, and the detailed mesophase behaviors were
confirmed by polarizing optical microscope (POM), and the
temperature-variable X-ray diffraction (XRD) studies (see
Supporting Information Figure 1a and Figures S3-S5). For GNRs,
the water-soluble precursor cetyltrimethylammonium
bromide-capped GNRs (CTAB-GNRs) were firstly synthesized by
the seed-mediated growth method,10 and then organosoluble
M-GNRs were subsequently obtained by the thiol exchange
for the stabilization of the BP I could be depicted as in Figure 3
.
The introduction of M-GNRs in the BPs might not only
suppress the volume and the free energy around the
disclination region of the lattices, but also result in stronger
intermolecular interactions between LC components,
especially when the temperature was close to BP I-cholesteric
phase transition, consequently stabilizing nanostructure over a
wider temperature range. However, the cubic superstructures
of BP I may be disrupted after the critical concentration of M-
GNRs was reached, thus at higher doping level, on the contrary,
restrained the BP I temperature range.
reaction with mesomorphic surfactant
5 in tetrahydrofuran,
where the surface of GNRs is covalently coated by the
mesogen monolayer. As expected, the resultant M-GNRs were
highly soluble in organic media because of the optimized
mesogen functionalization (Figure S6). The UV-Vis-NIR
spectrum of as-prepared M-GNRs exhibits the characteristic
longitudinal and transverse absorption signals, which are
similar to the CTAB-GNRs (Figure 1b).11 The transmission
electron microscopy (TEM) image clearly indicates the nearly
uniform size and morphology of M-GNRs with an average
aspect ratio of ~ 3.1 (length 44.9 ± 4.9 nm; width 14.8 ± 1.9
nm).
LC molecules
Double-twist cylinder
M-GNRs
Figure 2a shows the temperature dependence of the
selective reflection wavelength in pure BP medium upon
cooling at a rate of 0.1 oC/min. The reflection wavelength
abruptly jumps from 494 nm to 551 nm at the BP II to BP I
Double twist arrangement
Cubic symmetry
Figure 3. Schematic illustration of self-organized body-centered cubic
nanostructure in BP I stabilized by anisotropic plasmonic M-GNRs
.
o
phase transition at 43.5 C. The maximum wavelength of ~610
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Figure 4a illustrates the typical textures of BPs doped with with 808 nm NIR laser, the platelet textures initially changed
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0.07 wt% M-GNRs in 10 μm thick untreated cell at a cooling from BP I to BP II in 30 s and then cleaDreOdI: 1in0.t1o03t9h/Ce5iCsCo0tr6o14p6icF
o
rate of 0.1 C/min, which were captured by using a crossed state within 60 s, whereas the reverse process occurred upon
POM in transmission mode. On cooling from isotropic phase, removing the NIR irradiation. This combined photoirradiation
o
BP II firstly appeared at 46.4 C and then transformed into BP I and subsequent thermal relaxation process was reversible and
at 44.1 oC. As the temperature was further decreased to 37.2 reproducible for many cycles without noticeable degradation.
oC, the phase completely changed into the cholesteric phase. By contrast, the above BP I without M-GNRs, i.e. pure BP host,
Additionally, the BPs formed the characteristic platelet did not transform into the isotropic phase upon the NIR
textures, and the reflection color gradually changed to a longer irradiation even for more than five minutes. Such a significant
wavelength with decreasing temperature. According to the difference is believed to result from the localized heating
Bragg’s law, the photonic reflection of BPs occurs in particular caused by photothermal effect of M-GNRs under the NIR laser
directions due to their periodic cubic nanostructures when irradiation. Figure 5b schematically illustrates the possible
illuminated by a monochromatic light with the wavelength transformation of self-organized photonic superstructures. The
comparable to lattice constant.Different from the X-ray 3D soft nanostructure transforms from body-centered cubic to
diffraction technique applied for chacterizing the structure of simple cubic symmetry and finally changes into the isotropic
conventional crystals, optical Kossel diffraction diagrams have phase upon the NIR laser irradiation, and it would relax back to
been typically used to index the types of cubic BP lattices the initial state on removal of the NIR-light owing to the bulk
(more details in Supporting Information).14 To further verify heat diffusion.
the BP lattice structures, Kossel diagram of BPs with 0.07 wt%
M-GNRs in 10 μm thick planar cell was observed as shown in
Figure 4b. As expected, the isotropic phase does not yield any
Kossel diagram. A prominent circular pattern appeared in the
temperature range of BP II, which resulted from the (100)
lattice of the simple cubic BP II. As the temperature decreased
from BP II to BP I, the diffraction ring switched to characteristic
diamond-shaped pattern corresponding to (110) lattice of
body-centered cubic BP I. Here we note that the BP II
superstructure reappeared before transforming into the
isotropic phase if the temperature was increased from the BP I
state.
Figure 5. (a) Typical POM images of BPs doped with 0.3 wt% M-GNRs
in 10 μm thick untreated cell upon irradiation with 808 nm NIR laser (2
W); (b) Schematic illustration of the NIR-light tunable self-organized
soft photonic superstructures. The yellow dots represent the cross
section of GNR in the BP matrices.
Figure 6a illustrates the response time dependence of
photonic nanostructures on the temperature and the
concentration of M-GNRs. It was found that the response time
from the BP I to isotropic phase decreased significantly with
increasing the doped concentration of M-GNRs, and raising the
initial temperature also contributed to a reduction in the
response time. To be specific, it takes nearly five minutes for
the BPs with 0.01 wt% M-GNRs to transform from the BP I
Figure 4. (a) Typical textures of BPs doped with 0.07 wt% M-GNRs in
10 μm thick cell without alignment at a cooling rate of 0.1 C/min; (b)
The Kossel diagrams of BPs doped with 0.07 wt% M-GNRs in 10 μm
thick cell with planar alignment upon cooling, where the typical
diagrams indicate phase transitions from isotropic to BP II followed by
BP II to BP I transition.
where 
T = 5 oC to isotropic phase, whereas the response time
o
decreased apparently to 1 minute for 0.3 wt% M-GNRs.
Furthermore, the response time of the BPs with 0.3 wt% M-
GNRs decreased from 60 to 10 s when T was reduced from 5
o
to 1 C. The shift in the photonic bandgap upon NIR-light
irradiation was recorded using a spectrometer incorporated
into the POM under the reflection mode. The BP photonic
nanostructures loaded with 0.3 wt% M-GNRs were found to
exhibit the tunable NIR-light directed reflections as shown in
Figure 6b. A strong and narrow reflection centered at a
wavelength of 607 nm (red) was observed in the initial BP I
To explore the NIR-light responsive properties of the self-
organized photonic superstructures loaded with M-GNRs, the
hybrid BP mixtures in the 10 μm thick untreated cells were
cooled down from the isotropic phase to a stable BP I state
and then irradiated with a 808 nm NIR laser (2 W). Figure 5a
shows the typical texture changes of BPs doped with 0.3 wt%
M-GNRs under the NIR irradiation at a temperature (T) below
state, where

T = 5 oC. The reflection exhibited a significant
the isotropic clearing point (TIso), where 
T = TIso-T = 5 oC and
the characteristic BP I texture was observed. Upon irradiation
blue-shift while its intensity decreased apparently upon
irradiation with 808 nm NIR laser, and the center wavelength
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a) T.-H. Lin, Y. Li, C.-T. Wang, H.-C. Jau, C.-W. Chen, C.-C. Li,
2
shifted to 560 nm (green) in 10 s. Interestingly, the reflection
abruptly jumped to 491 nm (blue) around 15 s because of the
phase transition from BP I to BP II. Thus dynamic red, green
and blue color reflections were achieved from the BP by NIR
laser irradiation for the first time. Longer irradiation with NIR-
light only resulted in a continuous decrease in reflection
intensity at the BP II state and, as expected, the reflection
completely disappeared after the sample transformed into the
isotropic phase.
H. K. Bisoyi, T. J. Bunning, Q. Li, Adv. Mater. 20V1ie3w, Article Online
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Figure 6. (a) Response time-dependence on the temperature and the
concentration of M-GNRs. Note: T = TIso-T, where TIso is the isotropic
clearing point of LCs; (b) Reflection spectra of BPs doped with 0.3 wt%
M-GNRs upon irradiation with 808 nm NIR laser.
,
;
,
In conclusion, a NIR-light-responsive self-organized 3D
photonic superstructure was fabricated by incorporating new
hydrophobic mesogen-functionized GNRs into a BP LC medium
composed of commercially available components. The
introduction of M-GNRs was found to be beneficial in
stabilizing the cubic nanostructure. Importantly, the resultant
3D photonic nanostructures could be switched between body-
centered cubic and simple cubic symmetry under the
irradiation of 808 nm NIR laser due to the significant
photothermal effect from M-GNRs. The reverse process occurs
upon removal of the NIR laser irradiation. This is the first
observation of BP phase transition enabled by NIR light.
Furthermore, reversible dynamic NIR-light-directed red, green,
blue (RGB) reflections of the light-driven 3D soft photonic
crystals were for the first time demonstrated. The results of
this research reported here are expected to provide a route to
spatially and temporally manipulate the 3D self-organized
nanostructures and their dynamic photonic properties, thus
paving way to cost-effective large-scale 3D photonic crystals in
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a
remotely programmable technique and leading to
applications in areas of optical devices and critical components
for next-generation of optical communication technology.
Q. Li thanks the AFOSR (FA9950-09-1-0254 and FA9550-12-
1-0037) and the CONACyT Scholarship 211982 to KGC. ODL
thanks the NSF DMR 1121288. GS and SK’s X-ray diffraction
was supported by the NSF under its US Ireland R&D
Partnership grant DMR-1410649. The TEM data were obtained
at the (cryo) TEM facility at the Liquid Crystal Institute, Kent
State University, supported by the Ohio Research Scholars
Program Research Cluster on Surfaces in Advanced Materials.
Notes and references
1
a) Q. Li (Ed.), Intelligent Stimuli-Responsive Materials: From
Well-Defined Nanostructures to Applications, John Wiley &
Sons, Hoboken, New Jersey, 2013; b) L. Wang, Q. Li, Adv.
Funct. Mater. 2015, 25, DOI: 10.1002/adfm.201502071.
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