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Cite This: ACS Omega 2018, 3, 9658−9674 http://pubs.acs.org/journal/acsodf

Achieving Color and Function with Structure: Optical and Catalytic

Support Properties of ZrO2 Inverse Opal Thin Films
Geoffrey I. N. Waterhouse,*,†,‡,§ Wan-Ting Chen,†,‡,§ Andrew Chan,†,‡,§
and Dongxiao Sun-Waterhouse†
†
School of Chemical Sciences, The University of Auckland, Auckland 1010, New Zealand
‡
The MacDiarmid Institute for Advanced Materials and Nanotechnology, Wellington 6140, New Zealand
§
The Dodd-Walls Centre for Photonic and Quantum Technologies, Dunedin 9054, New Zealand
*
S Supporting Information

ABSTRACT: Taking inspiration from natural photonic

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crystal architectures, we report herein the successful

fabrication of zirconia inverse opal (ZrO2 IO) thin-film
photonic crystals possessing striking iridescence at visible
wavelengths. Poly(methyl methacrylate) (PMMA) colloidal
from https://pubs.acs.org/doi/10.1021/acsomega.8b01334.

crystal thin films (synthetic opals) were first deposited on

glass microscope slides, after which the interstitial voids in the
films were filled with a Zr(IV) sol. Controlled calcination of
the resulting composite films yielded iridescent ZrO2 IO thin
films with pseudo photonic band gaps (PBGs) along the
surface normal at visible wavelengths. The PBG position was dependent on the macropore diameter (D) in the inverse opals
(and thus proportional to the diameter of the PMMA colloids in the sacrificial templates), the incident angle of light with
respect to the surface normal (θ), and also the refractive index of the medium filling the macropores, all of which were
accurately described by a modified Bragg’s law expression. Au/ZrO2 IO catalysts prepared using the ZrO2 IO films
demonstrated outstanding performance for the reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4, which
can be attributed to the interconnected macroporosity in the films, which afforded a high Au nanoparticle dispersion and also
facile diffusion of 4-nitrophenol to the catalytically active Au sites.

1. INTRODUCTION the display feathers of the peacock (Pavo cristatus) contains 2D

Intriguing, ingenious, and diverse are the mechanisms by which
nature uses submicron-scale periodic architectures called
photonic crystals to create structural color.1−14 A characteristic
feature of structurally colored materials is their iridescence or
color change with viewing angle with respect to a fixed white
light source (cf. pigment-based colored materials that generally
look the same color at all illumination and viewing angles).
The striking iridescence shown by photonic crystals arises from
the selective diffraction of certain wavelengths of white light on
one-dimensional, two-dimensional (2D), or three-dimensional
(3D) periodic structures within the material, where typically
the periodicity is comparable to visible wavelengths (400−700
nm). Figure S1 shows digital photographs for some common
naturally occurring structurally colored objects, as well as
scanning electron microscopy images of the periodic dielectric
structures responsible for the iridescent colors of these objects.
These examples serve to highlight key concepts exploited here
in our research aimed at the fabrication of ZrO2 inverse opal
thin-film photonic crystals. In Paua shell (Haliotis iris), 400
nm-thick tiles of calcium carbonate add mechanical strength to
the molluscs shell, but also cause the shell to diffract strongly at
both near-infrared (first-order diffraction) and visible (second-,
third-, and fourth-order diffraction) wavelengths.12 The eye in
arrays of melanin rods, with the diameter of the rods
depending on the location in the eye (rods in the green part
have a diameter of around 140 nm, whereas rods in the orange
part have a slightly larger diameter of ∼150 nm).13 Finally,
precious opal obtains its color from a face-centered cubic (fcc)
(3D) arrangement of monodisperse spherical silica (SiO2)
colloids, with colloid diameters typically in the range 200−300
nm.14 The diffracted wavelengths in opals increase with colloid
diameter (i.e., at normal incidence, opals made of 200 nm
colloids reflect in the violet, those made from 250 nm colloids
in the green, and those made from 300 nm colloids in the red).
Light refraction and diffraction leading to color in opal-based
photonic crystals are depicted in Figure S2 and have been
discussed in depth below.15−24 In each of the examples in
Figure S1, a dark background provided by protein or a
sandstone matrix enhances the color play of the photonic
crystal architecture, making the iridescence more vivid. These
are but a brief snapshot of the diverse architectures used in
nature to generate structural color. Physicists and engineers are
Received: June 13, 2018
Accepted: August 9, 2018
Published: August 21, 2018

© 2018 American Chemical Society 9658 DOI: 10.1021/acsomega.8b01334

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now using “top-down” approaches25−28 and chemists and
biologists are using “bottom-up” approaches29−69 to fabricate
photonic crystals operating at near-infrared wavelengths (for
optical communications, especially waveguides, fiber-optic
cables, fast optic switches, etc.) and visible wavelengths
(sensing, high-efficiency laser cavities). Nature serves as a
valuable teacher for technology breakthroughs in these areas.
Among the methods used by chemists for photonic crystal
fabrication, the colloidal crystal template approach is arguably
the most popular due to the diverse range of photonic crystals
that can be obtained.42−69 The first step in this approach is the
synthesis of monodisperse polymer or silica colloids via
surfactant-free emulsion polymerization or the Stö ber
method,30−33,42,48 respectively, followed by the crystallization
of these colloids to form a colloidal crystal or synthetic opal
(typically a face-centered cubic array of colloids with a solid
fraction of 74 vol %). Due to the high interfacial surface free
energies of submicron-sized spherical colloids, polymer and
silica colloids tend to spontaneously self-assemble to form well-
ordered colloidal crystals, which assists this fabrication route.
Strategies used to form colloidal crystals from aqueous or
ethanoic colloidal dispersions include gravitational sedimenta-
tion, centrifugation, evaporation, and various “falling meniscus”
methods.33−42,70−74 The latter methods are especially ame-
nable for colloidal crystal thin-film deposition on planar
substrates (this is preferable if detailed optical analyses are
going to be performed on the colloidal crystals and their
inverted replicas). In the subsequent stage of the colloidal
crystal templating strategy, the colloidal crystal (i.e., opal) is
used as a sacrificial template to fabricate inverse opal replicas,
comprising a face-centered cubic array of air spheres
(macropores) in a solid matrix.42−69 To obtain the inverse
opal, the interstitial voids in the colloidal crystal template (26
vol % of the structure) are filled with a solid material via sol−
gel, electrochemical, or nanoparticle infiltration methods, after
which the original colloidal crystal template is selectively
removed by dissolution or calcination (heating in air). A
multitude of inverse opal-based photonic crystal materials have
been synthesized by this strategy, including metals, metal
oxides, conducting polymers, and carbon materials.29,42−69 The
three-dimensionally ordered macroporous structure of inverse
opals, together with their inherent photonic crystal properties,
creates new opportunities in optical sensor development,
separation, photocatalysis, and catalysis, among others.
Particularly valuable in this context are inverse opal thin
films suitable for “on chip” diagnostic or sensing applications,
though reliable design strategies toward large-area inverse opal
thin films are currently limited, prompting further research in
this area.
In response, our group has been targeting new and approved
approaches toward inverse opal thin films, primarily metal
oxides42,62−66 and conducting polymers.67−69 Zirconia (ZrO2)
attracts particular interest owing to its high thermal stability
and chemical inertness, leading to end applications in high-
performance ceramics, catalysis, sensing, and high-temperature
fuel cell applications.48,49,75−80 Herein, we report the first
successful fabrication and detailed optical characterization of
ZrO2 inverse opal thin films. Evaluation of the performance of
the zirconia inverse opal (ZrO2 IO) films for refractive index
sensing and catalytic applications was a further aim of the
research. At this point, it should be mentioned that most of the
methodologies introduced here for the fabrication and
characterization of the ZrO2 IO thin films were developed in
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undergraduate teaching labs in Advanced Physical Chemistry
(CHEM 310) and Materials Chemistry (CHEM 380) at the
University of Auckland. Indeed, 4−12 weeks undergraduate
research projects based on photonic crystal fabrication by the
colloidal crystal template method have proved extremely
popular with final year BSc students and honors program
students, offering a rich tapestry of open-ended learning
experiences that encompass, but are not limited to, emulsion
polymerization for polymer colloid synthesis, colloid crystal-
lization techniques, colloidal crystal templating strategies, sol−
gel chemistry, optical characterization techniques (UV−vis
transmittance and reflectance), computational modeling of
photonic band-gap structures, as well as hands-on exposure to
advanced characterization techniques not normally accessed by
undergraduates (scanning electron microscopy (SEM)/energy-
dispersive spectrometry (EDS), transmission electron micros-
copy (TEM), X-ray diffraction (XRD), X-ray photoelectron
spectroscopy (XPS), N2 physisorption). Parallel research
around natural structurally colored materials such as iridescent
beetles, bird feathers, and so forth has allowed students to
greatly extend their knowledge of color and how it is generated
(i.e., extending beyond the norms such as pigment-based color,
transition-metal complexes, charge-transfer complexes, fluo-
rescence and phosphorescence, chemiluminescence), culmi-
nating in enhanced student interest in higher postgraduate
programs. Methodologies introduced here for inverse opal
thin-film fabrication are designed to be easily adopted
elsewhere to enhance chemistry-based teaching programs.
2. EXPERIMENTAL SECTION
2.1. Materials. Methyl methacrylate (99%, Aldrich), 2,2′-
azobis(2-methylpropionamidine) dihydrochloride (97%),
zirconium(IV) propoxide (70 wt % in 1-propanol), concen-
trated HCl (37 wt %), tetrachloroauric acid trihydrate
(≥99.8%), urea (99%), sodium borohydride (%), and 4-
nitrophenol (%) were all obtained from Sigma-Aldrich and
used without further purification. Methanol (99%), ethanol
(99.4%), acetone (99%), n-heptane (99.5%), benzene (99.7%),
dichloromethane (99%), carbon tetrachloride (99.5%), toluene
(98%), and bromobenzene (95%) were obtained from local
suppliers. Milli-Q water (18.2 MΩ cm resistivity) was used in
all experiments.
2.2. Synthesis of Monodisperse Poly(methyl meth-
acrylate) (PMMA) Colloids. Three batches of monodisperse
PMMA colloids with diameters of 317, 360, and 441 nm
(denoted PMMA #1, PMMA #2, and PMMA #3, respectively,
in the text below) were synthesized by the surfactant-free
emulsion polymerization of methyl methacrylate at temper-
atures between 70 and 80 °C (Table S1, Figure S3), following
procedures introduced by Schroden et al. with a few
modifications.48 Briefly, a volume of methyl methacrylate
(0.3 or 0.4 L depending on the batch) and water (1.6 L) was
heated under vigorous mechanical stirring and a N 2
atmosphere to the desired reaction temperature (70, 75, or
80 °C). Subsequently, 2′-azobis(2-methylpropionamidine)
dihydrochloride (1.5 g) was quickly added to initiate the
polymerization reaction, which was then continued for 3 h at
the specified reaction temperature. Finally, the PMMA colloid
suspensions were quickly cooled to room temperature, filtered
through glass wool, and stored in glass Schott bottles for later
use.
2.3. Fabrication of PMMA Colloidal Crystal Thin
Films. PMMA colloidal crystal (PMMA CC) thin films on
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Figure 1. SEM images for the PMMA colloidal crystal films viewed along the [111] direction. (a, b) PMMA CC #1; (c, d) PMMA CC #2; and (e,
f) PMMA CC #3. Images on the left were taken at 20 000× magnification, those on the right at 100 000× magnification. The insets in (a), (c), and
(e) show Fourier transforms of the corresponding image and confirm a high degree of structural order.

glass microscope slides were fabricated using the flow-
controlled vertical deposition (FCVD) method outlined in
Figure S4a,b. Briefly, 20−25 mL of the PMMA colloid
suspensions obtained in Section 2.2 was diluted with water to a
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volume of 500 mL, which was then poured into a vertical-
walled glass beaker. Glass microscope slides were then
immersed vertically in the diluted colloid suspension, after
which a peristaltic pump slowly removed the colloidal
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Table 1. Summarized Structural and Optical Data for the PMMA Colloidal Crystal Films and Their ZrO2 Inverse Opal
Replicasa
−1
sample 2
BET surface area (m g ) DSEM (nm) b
DUV−vis (nm)
PMMA CC #1 317 319
PMMA CC #2 360 362
PMMA CC #3 441 439
ZrO2 IO #1 47.7 260 242
ZrO2 IO #2 44.9 287 281
ZrO2 IO #3 47.6 342 345
a
D = center-to-center distance between spheres on fcc (111) planes. bDUV−vis, navg, and ϕ determined from plots of λmax2 versus sin2 θ.
suspension (pump rate about 0.3 mL min−1). As the meniscus
of the colloid suspension moved down the glass slide, colloidal
crystals of thickness 5−7 μm (18−25 layers of colloids) were
deposited. In general, the FCVD method proved superior to an
evaporation method (Figure S4c) also trialed for colloidal
crystal fabrication.
2.4. Fabrication of Zirconia Inverse Opal Thin Films.
ZrO2 IO thin films were prepared using the colloidal crystal
templates fabricated above. Briefly, a Zr(IV) sol was first
prepared by adding Zr(IV) propoxide in 1-propanol (5 mL) to
5 mL of methanol under vigorous stirring, followed by the
addition of concentrated HCl (2 mL) and water (2 mL). The
resulting mixture was stirred for 30 min to give a clear and
homogeneous sol, after which it was diluted 5-fold with
methanol. For the colloidal crystal infiltration step, the coated
glass slides were placed on a slight incline (∼5°), after which
3−4 drops of the diluted Zr(IV) sol were placed on the
uppermost edge of the colloidal crystal film. Gravity and
capillary action then allowed the sol to infiltrate all the
interstitial spaces in the film. After hydrolyzing and drying for
24 h at room temperature, the resulting ZrO2/PMMA CC
composites were then calcined using the following protocol:
heating from room temperature to 300 °C at 2 °C min−1,
holding at 300 °C for 2 h, heating from 300 to 400 °C at 2 °C
min−1, then holding at 400 °C for 2 h. Finally, the films were
cooled to room temperature and then subjected to detailed
characterization.
2.5. Fabrication of Au/ZrO2 IO Catalysts. Gold
nanoparticles were deposited on ZrO2 IO films at nominal
weight loadings of 5 and 18 wt % using a modified version of
the procedure described by Zanella.81 Briefly, the ZrO2 IO
films were immersed in a 100 mL aqueous solution containing
a certain amount of HAuCl4·3H2O and urea (1 g) and then
heated to 80 °C and kept at this temperature for 4 h. By
increasing the amount of HAuCl4·3H2O in the solution, the
amount of gold deposited on the films could be systematically
increased. After reaction for 4 h, the films were rinsed with
water, dried in air at 90 °C, and then heated to 300 °C for 1 h
to reduce adsorbed Au(OH)3 or Au2O3 to metallic Au0
nanoparticles.
2.6. Characterization. SEM micrographs were taken using
a Philips XL-30S Field Emission Gun scanning electron
microscope (FEGSEM) operated at an electron accelerating
voltage of 5 kV in high vacuum. Prior to analysis, specimens
were mounted on black carbon tape and sputter coated with
platinum for 60 s with a Quorum Q150RS.
TEM images were collected on a Tecnai T12 transmission
electron microscope operating at an accelerating voltage of 120
kV, equipped with a 4 megapixel camera. Specimens were
dispersed in ethanol, and then a drop of the resulting
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optical data and derived constantsb
navg ϕ λmax (nm) θ = 0° Δλ/λmax a/λmax
1.35 0.72 707 0.073 0.63
1.36 0.72 802 0.074 0.63
1.37 0.74 983 0.074 0.64
1.16 0.16 462 0.125 0.79
1.15 0.15 526 0.120 0.77
1.12 0.12 635 0.128 0.77
dispersion was placed on a holey carbon-coated copper TEM
grid. The ethanol was then allowed to evaporate at room
temperature for several hours before sample imaging.
X-ray powder diffraction patterns were obtained on a
Siemens D5000 X-ray diffractometer equipped using a Cu Kα1
source (λ = 1.5418 Å, 40 mA, 40 kV). Data were collected over
the 2θ range of 2−100°, with a step size of 0.02° and a scan
rate of 2° min−1. ZrO2 crystallite sizes (L) were estimated from
the X-ray powder diffraction data using peak line widths and
the Scherrer equation.82
XPS data was collected on the soft X-ray Beamline at the
Australian Synchrotron. The endstation was equipped with a
hemispherical electron energy analyzer and an analysis
chamber of base pressure ∼1 × 10−10 Torr. Spectra were
excited using monochromatic Al Kα X-rays (1486.69 eV).
Core-level scans were collected over the Zr 3d and Au 4f
regions with an analyzer pass energy of 20 eV. The binding
energy scale was calibrated against the C 1s signal at 285.0 eV
from adventitious hydrocarbons.
N2 physisorption isotherms for the ZrO2 inverse opals were
collected at 77 K on a Micromeritics TriStar 3000. Specific
surface areas and pore sizes were calculated from N2
physisorption isotherms according to the Brunauer−Em-
mett−Teller (BET)83 and Barret−Joyner−Halenda84 methods.
Prior to analysis, samples were heated at 180 °C overnight in a
vacuum oven.
UV−vis transmittance spectra for the PMMA colloidal
crystal films and ZrO2 inverse opal films were recorded over
the wavelength range 300−1100 nm on a Shimadzu UV-1700
spectrometer, equipped with a custom-built sample holder for
UV−vis transmittance measurements at different film angles to
the sample beam path.
The photonic band-gap structure diagram for the ZrO2 IO
films was created using the MIT photonic-band package. Fully
vectoral eigenmodes of Maxwell’s equations with periodic
boundary conditions were computed by preconditioned
conjugate-gradient minimization of the block Rayleigh
quotient in a planewave basis, along the high-symmetry
directions U-L-Γ-X-W-K for an fcc first Brilluoin zone.85 The
additional parameters for ZrO2 calculations are as follows:
rsphere = 1.06 and neff = 2.1.
2.7. Catalytic Activity Tests. The reduction of 4-
nitrophenol at room temperature with sodium borohydride
(NaBH4) as the reductant was used to test the activity of the
ZrO2 IO and Au/ZrO2 IO catalysts. In a typical experiment,
catalyst (2 mg) was added to aqueous 4-nitrophenol (0.15
mM, 25 mL) with stirring. Then, 2.75 mL of the resulting
dispersion was added to a standard quartz cuvette (path length
1 cm). To start the reaction, 0.25 mL of freshly prepared
NaBH4 (0.1 mol L−1) was then added. The reaction progress
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Figure 2. UV−vis transmittance spectra collected in air at incident angles of 0, 5, 10, 15, 20, and 25° with respect to the [111] direction for (a)
PMMA CC #1; (b) PMMA CC #2; and (c) PMMA CC #3. As the incident angle of light increased from 0 to 25°, the [111] PBGs blue-shifted in
accordance with eq 2. (d) Plot of λmax2 versus sin2 θ for the PMMA CC films.
was monitored by collecting UV−vis absorption spectra every
30 s from 250 to 600 nm. The absorbance at 400 nm was
monitored as a function of time, and pseudo-first-order rate
constants (k′) for the reduction of 4-NP were calculated from
the slopes of plots of ln(At/A0) versus t.
3. RESULTS
3.1. Structural and Optical Characterization of the
PMMA Colloidal Crystal Films. The colloidal crystal
template technique relies heavily on the synthesis of
monodisperse spherical colloids and their subsequent self-
assembly to form well-ordered colloidal crystals. Accordingly,
preliminary SEM and UV−vis characterization studies were
performed on PMMA CC #1, PMMA CC #2, and PMMA CC
#3 thin films to assess their suitability as templates for ZrO2
inverse opal fabrication. Figure 1 shows the SEM images along
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the [111] direction for films fabricated from each PMMA
colloid batch. In each case, the films crystallized with their fcc
(111) planes parallel to the underlying glass substrate. Further,
each batch was found to be highly monodisperse, with all
colloids in each batch having the same size resulting in very
sharp spots in the Fourier transforms performed on the SEM
images (see insets in Figure 1a,c,e). In the higher magnification
images, small necks can be seen between neighboring colloids,
which likely formed during the drying of the colloidal crystals.
This necking adds a degree of mechanical strength to the
PMMA colloidal crystals, which is beneficial for colloidal
crystal templating (see below). The diameters of the colloids,
calculated as the center-to-center distance between adjacent
colloids on the (111) planes, were 317, 360, and 441 nm for
PMMA CC #1, PMMA CC #2, and PMMA CC #3,
respectively (Table 1). The colloidal crystal films developed
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Figure 3. SEM images for ZrO2 inverse opal films viewed along the [111] direction; (a, b) ZrO2 IO #1; (c, d) ZrO2 IO #2; and (e, f) ZrO2 IO #3.
Images on the left were taken at 50 000× magnification and those on the right at 100 000× magnification. The insets in (a), (c), and (e) show
digital photographs of the ZrO2 inverse opal thin films in air, illuminated and viewed along the [111] direction.

some cracks during fabrication and SEM imaging (Figure S5a) Colloidal crystal film thicknesses were typically in the range
but generally had very acceptable structural uniformity. of 5−7 μm (Figures S4d and S5b).
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Figure 4. (a−c) UV−vis transmittance spectra collected in air for the ZrO2 inverse opal films at incident angles of 0−25° with respect to the [111]
direction. The spectra were collected in 5° increments. (d) Plot of λmax2 versus sin2 θ for the ZrO2 inverse opal films. (e) Digital photograph of
ZrO2 IO #2 illuminated and viewed along the surface normal, and (f) the same film illuminated along the surface normal but viewed at an angle of
around 30° with respect to the surface normal.

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Figure 5. (a) Plot of position of the photonic band gap along the
[111] direction and the normalized band-gap width (Δλ/λ) versus
the center-to-center distance between macropores (D) on fcc (111)
planes in the ZrO2 inverse opal films. (b) Photonic band-gap structure
diagram for a ZrO2 inverse opal, showing a pseudo photonic band gap
at a/λ = 0.77 (indicated by the blue shaded area) between the second
and third bands along the fcc L → Γ direction.
The PMMA colloidal crystals all showed structural color,
especially when viewed at grazing angles that shifted their
photonic band gaps (PBGs) along the [111] and [200]
directions into the visible region. UV−vis transmittance spectra
for the PMMA colloidal crystal films collected along the [111]
direction, that is, normal to the (111) planes, are shown in
Figure 2. PMMA CC #1, PMMA CC #2, and PMMA CC #3
gave intense PBGs along the [111] direction (θ = 0°) at 707,
802, and 983 nm, respectively (Table 1). Note that here we
have collected transmittance spectra rather than reflectance
spectra, and as such the PBGs will appear as sharp dips in
transmittance (by convention we still use the term λmax here to
describe the PBG position). The shift in the PBG position
(λmax) to longer wavelengths with increasing colloid diameter
(D), and hence increasing interlayer spacing along the [111]
direction, is in perfect accord with predictions of the modified
Bragg’s law expressions below,48,63 which consider both
refraction and diffraction of light in opal-based photonic
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crystals (Figure S2). For first-order diffraction on any fcc plane
of an opal-based photonic crystal (including inverse opals), the
position of the PBG can be described by the following
equation
λmax = 2dhkl navg 2 − sin 2 θ (1)
where λmax is the PBG position (in nm), dhkl is the interlayer
spacing for a particular (hkl) plane, θ is the incident angle of
light with respect to the normal of the plane, and navg is the
average refractive index of the photonic crystal, typically
calculated as navg = [ϕnsolid + (1 − ϕ)nvoid], where ϕ is the solid
volume fraction and nsolid and nvoid are the refractive indices of
the solid and void components, respectively. Note for a PMMA
colloidal crystal in air with an ideal solid volume fraction of
0.74, navg = (0.74 × 1.492 + 0.26 × 1.00) = 1.364. For first-
order diffraction on fcc (111) planes, eq 1 transforms to eq 2
since d111 = 0.8165D.
λmax = 1.633D navg 2 − sin 2 θ (2)
When θ = 0°, eq 2 reduces further to
λmax = 1.633Dnavg (3)
Thus, the PBG position for first-order diffraction along the
[111] direction should be directly proportional to D (i.e., λmax
= 2.23 × D), in excellent accord with the shift in the PBG
position to longer wavelengths seen on going from PMMA CC
#1 to PMMA CC #3 (Figure 2 and Table 1). The normalized
PBG bandwidths (Δλ/λmax) and PBG angular frequencies (a/
λmax) were near identical for all three different colloidal crystals,
consistent with their identical construction (differing only in
the colloid diameter). As predicted by eq 2, the PBGs along
the [111] direction blue-shifted as the incident angle of light
with respect to the [111] direction increased (Figure 2). Plots
of λmax2 versus sin2 θ yielded straight lines (r2 > 0.995, Figure
2d). Values of D, navg, and ϕPMMA determined from the slopes
(−1.6332D2) and y-axis intercept (1.6332D2navg2) for the
colloidal crystal films were in excellent accord with expect-
ations (Table 1, columns 4−6).
3.2. Structural and Optical Characterization of ZrO2
Inverse Opal Films. After the colloidal crystal templating
step, brightly colored films were obtained, indicating the
success of the inversion process. Whereas the PMMA colloidal
crystals (opals) were constructed from solid spheres with air in
between, the inverse opal replicas comprised a face-centered
cubic array of air spheres (macropores) in a ZrO2 matrix
(Figure 3). When viewed along the [111] direction, the ZrO2
IO #1, ZrO2 IO #2, and ZrO2 IO #3 films appeared purple,
green, and orange, respectively. UV−vis transmittance spectra
collected along the [111] direction (θ = 0°) revealed band
gaps at 462, 526, and 635 nm (Figure 4), consistent with the
reflected color of each film. In agreement with eq 2, the PBG
along the [111] direction shifted to shorter wavelengths as the
incident angle of light was increased with respect to the [111]
direction. Values of D, navg, and ϕZrO2 obtained from plots of
λmax2 versus sin2 θ (Figure 4d) are listed in Table 1. Figure 4e,f
shows a ZrO2 IO #2 film illuminated and viewed along the
[111] direction and at an angle of 30° with respect to the angle
of illumination, respectively. Note the striking color change
with anglegraphic evidence for the successful realization of
structural color in the films.
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Figure 6. (a, b) UV−vis transmittance spectra collected along the [111] direction for different ZrO2 inverse opal thin films in air (n = 1.000) and
solvents of increasing refractive index (ranging from methanol, n = 1.329, to bromobenzene, n = 1.558). For both samples, the PBGs progressively
red-shifted as the refractive index of the solvent filling the macropores in the films increased. Insets in (a) and (b) shows contact angle data for a
water droplet on each ZrO2 IO film. The digital photographs below the spectra show each ZrO2 IO film in air and ethanol, separately.

As with the PMMA colloidal crystal templates, the PBG
position along the [111] direction for the ZrO2 IOs shifted to
longer wavelengths as D increased (Table 1 and Figure 5a).
The normalized PBG bandwidths (Δλ/λmax) and PBG angular
frequencies (a/λmax) were also very similar for the three
different samples, consistent with expectations for ZrO2 IOs of
comparable solid volume fraction (0.12−0.16). The a/λmax
value of 0.77 found for ZrO2 IO #2 and ZrO2 IO #3 agreed
perfectly with the value predicted in the photonic band-gap
structure diagram for a ZrO2 IO with a solid volume fraction of
around 0.12 (Figure 5b). In the diagram, a pseudo photonic
band gap opens between the second and third bands along the
L → Γ or [111] direction at a/λmax = 0.77, as indicated by the
blue shaded area.
It should be noted here that on transforming the PMMA
colloidal crystals to their inverse opal replicas, the center-to-
center distances between spheres on the fcc (111) planes
decreased by ∼18−22%. The theoretical maximum solid
volume fraction for the inverse opals is 0.26, but the actual
values were approximately one half of this (ϕZrO2 = 0.12−0.16).
The data suggests that the during the template removal
process, the films cracked and shrunk to form small islands on
the glass microscope slides, though clearly the islands retained
the desirable (111) orientation of the PMMA colloidal crystal
9666
templates (Figure 3). Further evidence in support of this
theory is found in the SEM images of Figure S5c−f, where an
island of ZrO2 IO is seen (Figure S5e). In addition, some
cracks and other defects can be seen in film cross sections
(Figure S5c,d), although these defects seem to have little
detrimental effect on the optical properties of the ZrO2 IO #2
film.
ZrO2 can exist in three different polymorphic forms,
monoclinic, tetragonal, and cubic, with the cubic form being
the most thermodynamically stable.86,87 Powder X-ray
diffraction patterns (Figure S6) for the ZrO2 IOs confirmed
that all were composed of tetragonal ZrO2 (space group P42/
nmc), consistent with the literature related to ZrO2 crystals
obtained by mild calcination of amorphous zirconia
precursors.86,87 The broadness of the XRD peaks is evidence
for the presence of nanocrystalline ZrO2 in the walls of the
inverse opals. Using the Scherrer equation,82 ZrO2 crystallite
sizes were estimated to be 3−5 nm. The ring structures seen in
the selected area diffraction pattern for ZrO2 IO #2 (Figure 8a)
validated this size estimate.
3.3. Refractive Index Sensing Using ZrO2 Inverse
Opal Films. One of the most fascinating and intriguing
features of the ZrO2 IO thin films was their dramatic color
change on being wetted by water or other liquids. As indicated
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Figure 7. Plot of the PBG position (λmax) along the [111] direction
versus the refractive index (nsolvent) of the solvent filling the
macropores in the ZrO2 inverse opal thin films. For all samples, a
strong linear relationship was observed (r2 > 0.999), in agreement
with eq 4.
in eqs 1−3, the photonic band-gap position (λmax) is highly
dependent on the average refractive index of the photonic
crystal. On filling the macropores in the ZrO2 IO films with
liquids of increasing refractive index, navg will increase, and thus
the PBG along the [111] direction is predicted to shift
progressively to longer wavelengths (i.e., red shift). Figure 6a,b
shows UV−vis transmittance spectra collected for ZrO2 IO #1
and ZrO2 IO #2 films, respectively, in air and then liquids of
increasing refractive index. Liquids used were methanol (n =
1.329), ethanol (n = 1.361), n-heptane (n = 1.388),
dichloromethane (n = 1.4241), carbon tetrachloride (n =
1.4601), benzene (n = 1.501), and bromobenzene (1.558). As
the refractive index of the liquid increased, the PBG along the
[111] direction shifted progressively to longer wavelengths.
The large change in the color of the ZrO2 IO #1 and ZrO2 IO
#2 films on going from air to ethanol is apparent in the digital
photos provided in Figure 6. ZrO2 IO #1 changed from purple
to yellow, and ZrO2 IO #2 changed from green to red. Once
the ethanol evaporated from the films, the original purple and
green colors of the films returned.
Surprisingly, the ZrO2 IO films were quite hydrophobic,
giving water droplet contact angles ranging from 120 to 124°
(Figure 6a,b, insets). These values were independent of the
macropore diameter in the ZrO2 IOs. By comparison, SiO2 IO
and TiO2 IO samples prepared by the same colloidal crystal
templating method (discussed briefly below) were hydrophilic
and easily wetted by water. This result suggests that the
combination of inverse opal structure (i.e., very spherical and
regularly sized macropores) and the unique physical properties
of the very small ZrO2 crystallites in the walls of the inverse
opals was responsible for the unexpected hydrophobicity
displayed by the ZrO2 IO films.88−90
Returning to the data in Figure 6a,b, we noted the PBG
positions for each ZrO2 IO in air and each liquid, which were
then used to create plots of PBG position versus solvent
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refractive index (Figure 7). The plots for all three ZrO2 IO
samples were remarkably linear (r2 > 0.999). This linearity can
be understood by substituting [ϕnsolid + (1 − ϕ)nvoid] for navg
in eq 3, which leads to the following equation
λmax = 1.633DϕnZrO2 + 1.633D(1 − ϕ)n void (4)
Here, nvoid represents the refractive index of the medium (i.e.,
solvent) filling the void space in the inverse opals. In
agreement with experimental observations, a plot of λmax
versus nsolvent is predicted to be linear, with slope = 1.633D(1
− ϕ) and y-axis intercept = 1.633Dϕ nZrO2. Using the slopes
and intercepts of the straight lines in Figure 7, we calculated
values of D and ϕZrO2 for the ZrO2 IO #1, ZrO2 IO #2, and
ZrO2 IO #3 films using the following expressions48,63
slope × nZrO2 + intercept
D=
1.633 × nZrO2 (5)
intercept
ϕ=
slope × nZrO2 + intercept (6)
Using nZrO2 = 2.1, the D values obtained were 251, 284, and
331 nm, respectively, and the ϕZrO2 values obtained were 0.158,
0.122, and 0.115, respectively, all in excellent accord with the
values determined for the same parameters using other
methods (Table 1). The very strong linearity of the plots in
Figure 7 suggested the ZrO2 IO films could be used in
refractive index sensing. To determine the refractive index of
an unknown liquid, all that would be required is to determine
the PBG position along the [111] direction using one of the
ZrO2 IO films. Once the PBG position was determined, the
refractive index of the unknown liquid could be extrapolated
from the plot in Figure 7 for that same ZrO2 IO or alternatively
calculated directly using the linear regression equation.
To test the sensitivity of the ZrO2 IO films for refractive
index sensing, we collected UV−vis spectra for the different
films in acetone (n = 1.3587) and ethanol (n = 1.3614), which
differ by only 0.0027 refractive index units. For the ZrO2 IO #1
film, a PBG shift to longer wavelengths of 1.2 nm was detected
on going from acetone to ethanol, with a slightly large shift of
1.4 nm found for the ZrO2 IO #2 film. Based on this result, we
thus estimate that the ZrO2 IO films should be able to discern
two liquids with a refractive index difference as small as 0.0005.
3.4. Optical Properties of Gold Nanoparticle-Deco-
rated ZrO2 Inverse Opal Films. Fascinated by the optical
properties of the bare ZrO2 inverse opal films, we decided to
explore this aspect further by decorating the films with gold
(Au) nanoparticles. Unlike bulk gold, which is yellow, gold
nanoparticles display a range of size-dependent colors due to
localized surface plasmon resonances (LSPRs).63,91,92 The
LSPRs are a collective oscillation of valence electrons on the
surface of the gold nanoparticles induced by the electric field of
light at the resonance frequency. For spherical gold nano-
particles of size <20 nm in water, the LSPR absorption
maximum is typically observed around 520 nm (i.e., the
nanoparticles absorb light strongly in the green part of the
visible spectrum), and we see the other reflected wavelengths
(especially the red part of the visible spectrum). For this
reason, a vial of small spherical Au NPs in water will look red
to the human eye. Similarly, stained glass windows containing
Au nanoparticles appear red to the observer. We were
particularly interested in decorating the ZrO2 IO #2 film
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Figure 8. (a, b) TEM images for ZrO2 IO #2 and (c, d) 5 wt % Au/ZrO2 IO #2. The images in (c) and (d) reveal well-dispersed Au nanoparticles
of size around 5−7 nm; (e, f) shows digital photographs of the 5 wt % Au/ZrO2 IO #2 film in air and after wetting with ethanol. The inset in (a)
shows a selected area diffraction pattern (scale bar = 0.2 Å−1). The well-developed ring structure confirms the presence of small nanocrystals of
tetragonal ZrO2 (P42/nmc).

with gold nanoparticles since that film has a PBG along the expected to absorb. This offered the opportunity to study two
[111] direction at 526 nm where the gold nanoparticles were competing optical phenomena (selective diffraction and
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Figure 9. (a) UV−vis transmittance spectra collected along the [111]
direction for a 5 wt % Au/ZrO2 IO #2 thin film in air (n = 1.000) and
solvents of increasing refractive index (ranging from methanol, n =
1.329, to benzene, n = 1.501). Both the PBG and the Au LSPR
progressively red-shifted linearly as the refractive index of the solvent
in the film increased, as shown in (b). The inset in (b) shows how the
hydrophobicity of the ZrO2 IO #2 film decreased after Au
nanoparticle deposition (top = before Au deposition; bottom =
after Au deposition).
reflection by the ZrO2 IO #2 film and strong absorption at
comparable wavelengths by the Au nanoparticles).
Figure 8 shows transmission electron microscopy (TEM)
images for the ZrO2 IO #2 film (Figure 8a,b) and the 5 wt %
Au/ZrO2 IO #2 film (Figure 8c,d). In both cases, the films
were scraped off the underlying glass substrate for imaging,
which did not adversely affect the ordered structure of the
films. The selected area diffraction pattern for the ZrO2 IO #2
film showed a characteristic ring structure, which supported
the earlier XRD findings that the films were composed of very
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small nanocrystalline tetragonal ZrO2 crystallites (<5 nm).
After decoration with Au nanoparticles at a loading of 5 wt %,
small Au nanoparticles of size 5−8 nm could be discerned in
the TEM images. The small size and excellent dispersion of the
Au nanoparticles over the ZrO2 IO support are consistent with
the known strong metal−support interaction between Au and
ZrO2. The XRD pattern for the 5 wt % Au/ZrO2 IO #2 film
(Figure S8) confirmed the successful deposition of Au
nanoparticles, with new broad peaks characteristic for small
Au crystals appearing (especially apparent in the XRD pattern
of the 18 wt % Au/ZrO2 IO #2 film, Figure S8). XPS data in
Figure S9 also confirmed the successful deposition of metallic
Au nanoparticles, with the Au 4f signal intensities increasing in
proportion to the nominal Au loadings. As expected, the Zr 3d
signals were attenuated slightly as the Au loading increased.
When illuminated and viewed along the [111] direction, the
Au/ZrO2 IO #2 film appeared green in air (Figure 8e). Thus,
the photonic crystal was rejecting wavelengths of light typically
used by the Au nanoparticles for absorption (i.e., the PBG
properties of the ZrO2 IO film appeared to dominate the
perceived color along the [111] direction; note: a noninverse
opal Au/ZrO2 specimen would certainly appear purple under
the same illumination conditions). On adding a drop of
ethanol to the film, the PBG for the 5 wt % Au/ZrO2 IO #2
film was red-shifted considerably and decoupled from the Au
LSPR, resulting in a brightly red-colored film (Figure 8f)
whose color is the sum of both PBG diffraction and Au LSPR
absorption.
The LSPRs of Au nanoparticles are known to be sensitive to
the refractive index of the surrounding medium91,92 and have
been used previously to develop refractive index sensors for
liquids. The data in Figures 6 and 7 revealed that the ZrO2 IO
films were extremely effective for refractive index sensing.
Accordingly, it was of novelty to see if the 5 wt % Au/ZrO2 IO
#2 film could be used to get a double determination of liquid
refractive index from a single UV−vis spectrum. Figure 9a
shows UV−vis transmittance spectra for the 5 wt % Au/ZrO2
IO #2 film in air (n = 1.000), methanol (n = 1.329), ethanol (n
= 1.362), n-heptane (n = 1.388), dichloromethane (n = 1.424),
carbon tetrachloride (n = 1.460), and benzene (n = 1.501). In
air, the ZrO2 IO #2 PBG along the [111] direction and the Au
LSPR absorption were almost perfectly overlapped, giving a
broad feature centered at 532 nm (i.e., responsible for the
green reflected color seen in Figure 8e). On immersion in the
various organic solvents, the Au LSPR and ZrO2 IO PBG
decoupled, giving two distinct features. The Au LSPR feature
was centered between 545 and 556 nm, and the ZrO2 IO #2
PBG centered between 663 and 754 nm. In both cases, these
features shifted linearly to longer wavelengths on increasing the
refractive index of the liquid the film was immersed in (Figure
9b). Accordingly, it can be concluded that the 5 wt % Au/ZrO2
IO #2 film allows two parallel determinations of the refractive
index of a liquid from a single UV−visible transmittance
spectrum measurement. Using the slope and intercept of the
PBG regression line in Figure 9b, values of D = 288.4 nm and
ϕZrO2 = 0.11 were calculated using eqs 5 and 6, respectively
(nZrO2 = 2.1 was assumed). These values are in good agreement
with data for bare ZrO2 IO #2 (D = 287 nm, ϕZrO2 = 0.15,
Table 1), indicating that gold Au nanoparticle deposition did
not really alter the geometric properties of the ZrO2 IO film
significantly.
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Figure 10. UV−vis absorbance spectra for aqueous solutions of 4-nitrophenol (0.15 mM, 2.75 mL) and NaBH4 (0.1 M, 0.25 mL) in the presence
of (a) ZrO2 IO #2; (b) 5 wt % Au/ZrO2 IO #2; and (c) 18 wt % Au/ZrO2 IO #3. (d) Plots of ln(At/A0) versus time.
3.5. Catalytic Activity of the Gold Nanoparticle-
Decorated ZrO2 Inverse Opal Films for 4-Nitrophenol
Reduction. As a further demonstration of the functionality of
the Au/ZrO2 IO #2 films fabricated in this study, we decided
to evaluate the catalytic activity of the as-prepared films, as well
as films decorated with Au nanoparticles at two different
loadings (5 and 18 wt %), for the reduction of 4-nitrophenol
using NaBH4 at the reducing agent.93,94 In the presence of a
large excess of NaBH4, the kinetics of this reaction, which is
catalyzed by metal nanoparticles, obeys pseudo-first-order
kinetics, as described by the following integrated rate law
ji A zy
lnjjj t zzz = −k′t
j A0 z
k {
(7)
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where At is the absorbance of the 4-nitrophenol solution in
water at 400 nm at time t, A0 is the initial absorbance of the 4-
nitrophenol solution in water at 400 nm (i.e., at t = 0 min), k′
is the pseudo-first-order rate constant (units min−1), and t is
the reaction time (in min). The reaction commences as soon
as the reducing agent (NaBH4) is added to the 4-nitrophenol
solution containing the catalyst. Figure 10a shows the UV−vis
absorption spectra for an aqueous solution containing 4-
nitrophenol, NaBH4, and ZrO2 IO. A gradual decrease in the
absorbance of the 4-nitrophenol peak at 400 nm is seen over
time (24 min), which can largely be attributed to 4-
nitrophenol adsorption on the ZrO2 IO surface (rather than
catalytic reduction). The rate constant of 0.026 min−1 was
understandably low. After decoration with Au nanoparticles,
known active catalysts for 4-nitrophenol reduction in the
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presence of NaBH4, the rate constant jumped dramatically to
k′ = 0.740 min−1 for the 5 wt % Au/ZrO2 IO #2 sample and
then to k′ = 1.927 min−1 for the 18 wt % Au/ZrO2 IO #2
sample. The evolution of the main reaction product, 4-
aminophenol, during the reaction is evident by the develop-
ment of the peak at 295 nm in the spectra. In the case of the 18
wt % Au/ZrO2 IO #2 sample, the reaction proceeded so
rapidly that it was almost impossible to follow by UV−vis
spectroscopy (reaching completion in 2 min). The rates
reported here accord well with the best literature data for 4-
nitrophenol reduction over the supported gold catalysts.94−97
This high activity can be understood in terms of the open
macroporous structure of the ZrO2 IO support that allows
facile transport of reagents to the Au active sites. The high gold
nanoparticle dispersion realized in the Au/ZrO2 IO system
(Figure 8c,d) is also advantageous in this context. Supported
Au nanoparticle catalysts offer many advantages over
unsupported Au nanoparticles in catalytic applications,
especially the stabilization afforded against nanoparticle
aggregation. After storage for 1 year at room temperature in
closed vials, the 5 wt % Au/ZrO2 IO #2 and 18 wt % Au/ZrO2
IO #2 catalysts demonstrated identical performance as the
freshly prepared catalysts for 4-nitrophenol reduction.
3.6. Author Commentary on the Versatility of
Colloidal Crystal Template Strategy. The data above
demonstrates the wonderful structural color palette that is
available by fabricating a single type of inverse opal film. By
varying the diameter of the PMMA colloids in the colloidal
crystal templates, it is possible to controllably modify the
position of PBGs along the [111] direction in the ZrO2 IO
films. By rotating the samples with respect to the source of
illumination, the PBG along the [111] direction can be shifted
to shorter wavelengths, and by filling the macropores in the
inverse opals with liquids of different refractive indices, it is
possible to redshift the PBG over a large range of wavelengths.
Through systematic manipulation of all of these parameters in
the current study, we have been able to recreate, via structural
engineering, all of the vivid colors exhibited by the natural
photonic crystal specimens in Figure S1. Importantly, all of the
optical phenomena we have reported relating to the ZrO2 IO
films are accurately captured by the modified Bragg’s law
expressions described in eqs 1−3. Further, by simply
substituting the Zr(IV) propoxide precursor with tetraethylor-
thosilicate or titanium (IV) propoxide and changing the
solvent from methanol to ethanol, keeping all other fabrication
procedures the same, amorphous SiO2 IO or nanocrystalline
TiO2 IO films, respectively, can readily be accessed (Figure
S10). All of the aformentioned aspects make colloidal crystal
templating a fascinating topic for advanced-level research as
well as undergraduate teaching laboratories. We encourage
others to enter this research space.
4. CONCLUSIONS
ZrO2 inverse opal thin films with striking angle-dependent
structural color at visible wavelengths were successfully
fabricated by the colloidal crystal template technique. The
optical properties of the films were dominated by first-order
diffraction on fcc (111) planes, with excellent accord
established between the optical properties of the films and
predictions based on a modified Bragg’s law expression.
Refractive index sensing with a sensitivity estimated around
∼0.0005 units was demonstrated using the ZrO2 inverse opal
thin films, based on the progressive linear shift in the PBG
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position along the [111] direction with increasing solvent
refractive index. Further, by functionalizing the ZrO2 IO films
with gold nanoparticles, a novel refractive index sensing
platform was created that allowed parallel determinations of
liquid refractive index (one strategy used the small shift in the
Au LSPR position, and the other utilized the large shift in the
PBG position as the refractive index of the solvent in the Au/
ZrO2 IO films increased). Due to their inherent macroporosity,
ZrO2 IOs represent near-ideal supports for noble metal
catalysts, which we confirmed through the successful
application of Au/ZrO2 IO films to the reduction of aqueous
4-nitrophenol in the presence of NaBH4. Results of this study
are expected to encourage others to utilize the colloidal crystal
template approach to fabricate novel photonic crystal thin films
for sensing and catalytic applications.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsome-
ga.8b01334.
Photos and SEM data for the selection of natural
photonic crystals; details of the equipment setups used
to synthesize the colloidal crystals and colloidal crystal
thin films; additional SEM data for PMMA colloidal
crystal films and their inverse opal replicas; UV−vis
transmittance spectra for the ZrO2 IO #1 and ZrO2 IO
#2 films in acetone and ethanol; XRD patterns for the
ZrO2 IO films and Au/ZrO2 IO catalysts; XPS data for
Au/ZrO2 IO catalysts; SEM data for SiO2 and TiO2
inverse opals (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: g.waterhouse@auckland.ac.nz. Tel: 64-9-9237212.
Fax: 64-9-373 7422.
ORCID
Geoffrey I. N. Waterhouse: 0000-0002-3296-3093
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Funding support from the MacDiarmid Institute for Advanced
Materials and Nanotechnology and the Dodd Walls Centre for
Photonic and Quantum Technologies is gratefully acknowl-
edged.
■
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9674 DOI: 10.1021/acsomega.8b01334

ACS Omega 2018, 3, 9658−9674