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Shaping the Emission Spectral Profile of Quantum Dots

with Periodic Dielectric and Metallic Nanostructures
Zhang-Kai Zhou, Dang Yuan Lei, Jiaming Liu, Xin Liu, Jiancai Xue, Qiangzhong Zhu,
Huanjun Chen,* Tianran Liu, Yinyin Li, Hongbo Zhang, and Xuehua Wang*

The emission profile and lifetime dynamics of semiconductor quantum dots

can be significantly shaped and altered using dielectric and plasmonic nanostructures based on anodic aluminum oxide templates. Remarkable spectral
modification and a large total decay rate enhancement in the photoluminescence of quantum dots are observed when they are deposited on a pristine
anodic aluminum oxide template. The modified emission spectral profile
is consistent with the calculated photonic local density of states above the
anodic aluminum oxide template surface, suggesting that this interesting
spectral tuning phenomenon stems from the surface electromagnetic modes
supported by the anodic aluminum oxide template. Furthermore, when the
anodic aluminum oxide template is loaded with metallic nanowires that sustain plasmon resonances, the photoluminescence of the quantum dots can
be largely enhanced. These unprecedented results suggest that the anodic
aluminum oxide template can be used as a versatile platform for tailoring the
photoluminescence properties of quantum emitters in future photonic and
optoelectronic applications.

Dr. Z.-K. Zhou, J. M. Liu, J. C. Xue, Q. Z. Zhu,

Prof. H. J. Chen, T. R. Liu, Prof. X. H. Wang
State Key Laboratory of Optoelectronic Materials
and Technologies
Sun Yat-sen University
Guangzhou, 510275, China
E-mail: [email protected];
[email protected]
Dr. Z.-K. Zhou, J. M. Liu, J. C. Xue, Q. Z. Zhu,
Prof. H. J. Chen, T. R. Liu, H. B. Zhang, Prof. X. H. Wang
School of Physics and Engineering
Sun Yat-sen University
Guangzhou, 510275, China
Prof. H. J. Chen
Guangdong Province Key Laboratory of Display Material and Technology
Sun Yat-sen University
Guangzhou, 510275, China
Y. Y. Li
State Key Laboratory for Biocontrol
School of Life Science
Sun Yat-sen University
Guangzhou, 510275, China
Prof. D. Y. Lei, Dr. X. Liu
Department of Applied Physics
The Hong Kong Polytechnic University
Hong Kong SAR, China

DOI: 10.1002/adom.201300354

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1. Introduction

Being referred to as artificial atoms

with atomic-like discrete energy levels,
semiconductor quantum dots (QDs) have
attracted growing research interest due to
their importance in fundamental research
and fascinating applications in novel photonic devices, such as qubits for quantum
information technology,[15] single-photon
emitters,[68] solar cells,[9,10] light-emitting diodes (LEDs),[11,12] and photodetectors,[13,14] to name a few. In addition, given
their size-dependent photoluminescence,
bright and stable emission, broad and
strong absorption, and excellent bioconjugation, the use of QDs in biological labeling and medical therapeutics has been
dramatically evolving.[1519]
The past decades have witnessed
increasing efforts on routing and tailoring
the light emission of semiconductor QDs
to unleash their full potential in future photonic and optoelectronic applications. Fluorescence intensity, emission direction,
polarization, and spectral profile are the four key properties enabling control over the light emission behaviors of the QDs. Up to
now, prevailing architectures for manipulation of these properties include subwavelength-scale structures made of dielectrics,
metals, or their hybrids.[2033] These architectures enable modulation of the photonic local density of states (PLDOS) in various
ways depending on their specific geometries and complex dielectric properties, giving rise to exceptional photoluminescence
behaviors of nearby emitters. For example, remarkable fluorescence enhancements have been observed by placing the QDs
in the vicinity of photonic crystals[22] or metallic nanostructures
supporting plasmon resonances.[29,30,34] Such enhancements
are due to the acceleration of excitation and emission rates of
the QDs by the photonic crystals or metallic nanostructures.
Besides intensity enhancement, the metal nanoparticles can
also strongly suppress the emission blinking for which QDs are
notorious.[35] In recent years, due to its importance in coherent
single-photon light sources for future high-speed quantum computing networks, tailoring the emission polarization and direction of the QDs has attracted more and more research interest.
So far this can be done with dielectric nanostructures,[36,37] photonic crystals,[3840] plasmon-based metal nanostructures,[41,42]
and nanoscale Yagi-Uda antennas.[43] Specifically, a recent
study demonstrated that an extremely narrow emission angle

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of 3.4 can be achieved through resonant coupling of the QDs'

2. Results and Discussion
optical transitions to a metallic nanoslit array.[41]
2.1. Fabrication and Characterization of the AAO Templates
In spite of these great progresses, the aforementioned
nanoscale architectures for tailoring QD emission often involve
complex fabrication techniques, such as photon lithography,
The AAO templates used in our study were prepared using a
electron-beam lithography, and focused ion beam milling, in
two-step anodization process.[50,51] After the ordered pores were
order to ensure their spatially varied dielectric permittivities or
formed, the underlying aluminum substrate was dissolved
precise geometries. These techniques are usually high cost and
using CuCl2 aqueous solution. Figure 1ac show the scanning
low throughput with a limited sample area. In addition, metallic
electron microscopy (SEM) images of a typical AAO template,
nanostructures usually suffer from intrinsic Ohmic losses,
which exhibit uniform pore size and a well-ordered array strucwhich has created severe challenges for their use in enhancing
ture. The average diameter of the pores and lattice constant of
or modulating the emission from QDs. Therefore a facile, lowthe template were measured to be 22 3 nm and 45 5 nm,
cost, and high-throughput platform with low optical absorption
respectively. It should be noted that the lattice constant of the
is in great demand for flexibly tailoring QD emission.
AAO template is defined as the distance between two adjacent
In comparison with the other three properties mentioned earpores with smallest separation (arrow b). In characterizations
lier, less focus has been laid upon the emission spectral profile of
of the cross section we need to cut off the AAO templates. Due
semiconductor QDs. Usually, QD emission is characterized by a
to different cleavage directions, lattice constants of different
Lorentzian-type profile associated with the transition between two
values can be obtained. For example, the distance between adjadifferent electronic energy levels. Changing of the local electrocent pores shown in Figure 1c is about 100 nm, which is the
magnetic environment around the QDs can significantly modify
diagonal length of the AAO lattice (arrow a in Figure 1a). If the
their different electronic transitions, whereby the overall emission
cleavage is along the direction indicated by arrow b, a lattice
spectrum is expected to be tailored. This is particularly important
constant of 45 nm can be obtained (Supporting Information
for the use of QDs in the fabrication of multicolor LEDs, which
Figure S1). The film thicknesses of the templates can be concan get rid of the complex and expensive color filters used curtinuously tailored without changing the diameter or period
rently in the LED industry. Furthermore, such multi-color emisby controlling the anodization time (Supporting Information
sion can promote biological imaging and labeling techniques.
Figure S2,S3). The optical properties of the AAO templates
Although similar phenomena have been well known in molecwere characterized by measuring their transmission spectra
ular systems,[4448] to the best of our knowledge, few studies have
at normal incidence. Figure 1d gives the representative transpaid attention to tackling this similar issue associated with QDs.
mission spectra of templates with three different thicknesses.
Very recently, plasmonic metamaterials were used to tailor the
A series of distinct transmission peaks/dips can be clearly
emission spectrum of semiconductor QDs, manifested by a narobserved in each spectrum, with the number of peaks/dips
rowing of the photoluminescence spectrum.[49]
increasing with the film thickness in the spectral range of
Here we propose a facile platform, the
anodic aluminum oxide (AAO) template, and
use it to tune the QD photoluminescence spectral profile. The AAO template was prepared
using a controllable, low-cost electrochemical
method. By measuring the photoluminescence
properties of the semiconductor QDs deposited onto the back side of the AAO template,
we show that the spectral profile and the photoluminescence lifetime of the QD emission
can be modified strongly through resonant
coupling of their emission energy with the
FabryProt modes excited in the AAO film.
Full-wave numerical calculations reveal that
the shaping of the emission spectrum is purely
due to the modulation of the PLDOS around
the AAO template, which also largely accelerates the total decay rates of an adjacent dipole.
In addition, direct loading of metallic nanorod
arrays into the AAO template further enhances
the photoluminescence intensity of the QDs
because of the plasmon-induced electromagnetic field enhancement. These interesting
Figure 1. SEM images and transmission spectra of the AAO templates. a,b) SEM images of a
findings open novel applications of the AAO
typical AAO template with viewing angles of 0 and 45, respectively. The arrows indicate two
templates in controlling the light emission of typical cleavage directions for the cross-section views. c) Cross-section view of the AAO temquantum emitters, which we believe will be of plate. The cleavage is along the direction indicated by arrow a. d) Transmission spectra of the
great importance in future QD photonics.
AAO templates with different thicknesses of 1.7 m (green), 5.2 m (red), and 6.9 m (blue).

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detection (Supporting Information Figure S2f). By extracting

the transmission peak positions 0 and the separation between
two adjacent peaks, , in each spectrum, we can determine the

value 8 82 to be constant. In addition, such a value is inversely
0
proportional to the film thickness of the template. These characteristics suggest that the oscillations in the transmission
spectra of the AAO templates originate from the FabryProt
mode interference, which states that the wavelength separation
between adjacent transmission peaks can be given as
8

820
2nl cos 2

(1)

where l is the thickness of the cavity, n is the refractive index,

and is the incidence angle. Taking the transmission spectrum
at = 0 for the film thickness of 1.7 m shown in Figure 1d,
the effective refractive index of the AAO template is calculated
to be 1.52, which is in the typical range of reported values.[52]
2.2. Emission Spectral Profile Shaping and Radiative Decay Rate
Engineering of QDs by Pristine AAO Templates
In our study, CdSe/ZnS core/shell QDs (Qdot@ 800 ITK
Streptavidin Conjugate Kit, Invitrogen Corporation) with an

average size of 12.0 0.5 nm are conjugated with streptavidin

to enable their dispersion in water.[53] In the photoluminescence experiment, the QDs were dispersed in deionized water
(8 nM) and subsequently drop-cast onto the back side of the
AAO template (see Figure 2a). Most of the QDs are shown to
homogeneously distribute onto the AAO template, as indicated
by the comparison between the SEM images of the pristine
template and template covered with QDs (Supporting Information Figure S4a,b). Due to the small size of the QDs and the
difficulty in focusing the electron beam for imaging on the
insulating and rough AAO template, it is hard to deduce the
QD density on the basis of Figure S4b. Therefore, we estimated
the QD area density when they were dispersed onto a silicon
substrate, which is around 1200 m2 (Supporting Information
Figure S4c). We chose not to deposit the QDs onto the opposite
side, i.e., making them face the pores. In such a manner, one
can avoid inhomogeneous fluorescence due to the diffusion of
the QDs into the pores at different depths.
Photoluminescence measurements were then utilized to
study the influence of the AAO template on the light emission
properties of the QDs. In the photoluminescence measurements, the excitation wavelength was 700 nm and a long-pass
filter with a cut-off wavelength at 750 nm was utilized to block
the laser line in collecting the emission spectra. Therefore only

Figure 2. Shaping the QD emission profile by FabryProt modes in the AAO templates. a,b) Schematic system showing the photoluminescence measurements of QDs on an AAO template (a), with the collected photoluminescence spectra of the QDs deposited on the AAO templates (dark blue) and
on quartz substrate (red) shown in (b). The film thicknesses, , of the AAO templates are 1.7 m and 5.2 m, respectively. The transmission spectra
of the pristine AAO templates are also included for reference (green). The photoluminescence spectra have been normalized for the purpose of clarity.
c,d) Schematic model used for calculating the radiation power of a dipole source located 10 nm above the AAO template (c), with the calculating results
shown in (d). The dashed blue lines in (c) draws a unit cell used in the simulations. e) Comparison of the photoluminescence decay dynamics of the
QDs on a quartz substrate and on AAO templates of various thicknesses. The collection wavelength is 790 nm. f) Calculated relative total decay rate of
the dipole on the AAO templates with different thicknesses. The dashed line indicates the wavelength where the experimental measurements were taken.

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(=

2T   2 
: D ( r 0 , T)
3g0

(2)


where
   T is the transition frequency, D (r 0 , T) is the PLDOS,
and :  is the transition dipole moment. In our study, the AAO
template serves equivalently as a photonic cavity with multiple
resonances, manifested by a series of transmission maxima. At
these resonances, the electromagnetic environment and therefore the PLDOS will be modified strongly. As a result, once coupled with the AAO template, the emission profile of the QDs is
modulated according to the transmission maxima that are in
resonance with the radiative electronic transitions of the QDs.
This is clearly manifested by the coincidence between the photoluminescence spectra (Figure 2b) and the calculated PLDOS

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the spectra above 750 nm were given. In order to have a systematic study, we prepared five templates of various film thicknesses ranging from 1.7 m to 6.9 m with a fixed pore size.
The emission spectra collected from QDs on two typical AAO
templates and on a quartz substrate are presented in Figure 2b,
along with the corresponding transmission spectra of the two
AAO templates. One can see that the emission spectrum of the
QDs on the quartz substrate shows a conventional Lorentzianshaped profile with an emission peak locating at 790 nm and
full width at half maximum (FWHM) of 92 nm. The relatively
broad emission spectrum stems from the inhomogeneous
broadening of the exciton line of the QDs due to their natural
size variation, and is strongly modified by the presence of the
AAO template. As shown in Figure 2b, the relatively broad
emission evolves into various photoluminescence peaks with
much smaller FWHM locating in the vicinity of the transmission maxima of the AAO templates. Most interestingly, with
increasing the template thickness, the number of transmission
maxima of the AAO template and therefore the narrowing of
the photoluminescence peaks of the QDs are increased (Supporting Information Figure S5). Such behaviors clearly indicate that the AAO templates coerce the QD emission into their
transmission profiles, and thus shape the corresponding emission spectra.
The spectral shaping effect was further analyzed via theoretical calculations, where the experimental system was modeled by placing a classical point dipole above the AAO template
(Figure 2c). The emission spectrum of the dipole is characterized by recording its radiation power, which is closely related
to the PLDOS at the dipole's location. Figure 2d shows the calculated emission spectra for the dipole placed on two templates
with film thicknesses of 1.7 m and 5.2 m, respectively, the
spectral profile of which are in excellent agreement with the
measured photoluminescence spectra of the QDs. Such spectral shaping is attributed to the resonant coupling of the QD
emission with the photonic cavity modes supported by the
AAO templates, which can accordingly modify the spontaneous
decay rate of the QDs. The QDs used in our study have a nominal quantum yield of 30%.[54] Due to the negligible absorption
of the AAO templates in the investigated spectrum range, in
the following analysis the change of the spontaneous decay rate
is approximated to be that of the total decay rate of the QDs
themselves. In quantumtheory, the spontaneous decay rate of
an emitter positioned at r 0 is expressed as[55,56]

distribution at the back side of the template (Supporting Information Figure S6), verifying that modification of the PLDOS
by the AAO template is responsible for the emission spectrum
reshaping of the semiconductor QDs.
The total decay rate (including nonradiative and radiative),
, of an emitter is the inverse of its emission lifetime. Thus,
the above observations from time-averaged photoluminescence
measurements can be further corroborated by time-resolved
photoluminescence measurements. Figure 2e presents the
transient photoluminescence measurements of the QD emission on different substrates. All of the fluorescence decay traces
were measured at 790 nm. The decay of the QDs on silica follows a single exponential function with a lifetime of 84.47 ns.
For QDs on the AAO templates, their photoluminescence decay
traces follow a two-component exponential behavior with the
form
IPL (t) = Af e t/tf + As e t/ts

(3)

where Af and As are the weight factors of the fast and slow processes, respectively. tf and ts are the corresponding lifetimes.
The lifetimes of the slow processes extracted from the measured intensity decay curves are the same as that of QDs deposited onto the quartz substrate, while the fast processes exhibit
much shorter lifetimes, as shown in Figure 2e. These findings
indicate that the spontaneous decay of the QDs is accelerated
by the AAO template due to the increase of the PLDOS. This
can be further unveiled by calculating the relative total decay
rate via normalizing the total radiation power of the dipole
source on the templates with that of the same dipole in free
space (Figure 2f). The calculated results show that the relative
total decay rates exhibit apparent oscillation behaviors synchronizing with the calculated emission spectra of the dipole. A
quantitative comparison can be made between the ratio of the
measured lifetimes for QDs on the three AAO templates and
that of the calculated relative total decay rates, where the measured 1/tf,1.7 m:1/tf,5.2 m:1/tf,6.9 m = 1:1.31:1.26 is very close to
the calculated relative total decay rate tot,1.7 m:tot,5.2 m:tot,6.9
m = 1:1.54:1.49 if the first term is normalized to 1 for comparison purpose. Most interestingly, both of the experimental
measurements and theoretical results show that the radiative
acceleration is most pronounced for QDs deposited on the
5.2 m-template. This is because, in such cases, the transmission maximum of the template at 790 nm coincides with the
intrinsic emission peak of the QDs, giving rise to the strongest
coupling between the template and QDs.
It is known that the photoluminescence bands of the QDs
are strongly dependent on their size. We want to point out that
the above emission spectral profile shaping effect is a general
behavior regardless of the size of the QDs we used. The spectral
shaping is due to the resonant coupling of the QDs emission
with the FabryProt interference supported by the AAO templates. The coupling strength depends on the spectral overlap
between the photoluminescence of the QDs and the Fabry
Prot interference of the AAO template. Therefore, once the
emission bands of the QDs lie within the wavelength range
where the FabryProt interference takes place, the spectral
shaping effect will still occur. We have measured the photoluminescence spectra of QDs with two different sizes deposited

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onto the AAO templates. The intrinsic emission peaks of these

two QDs samples locate at 607 nm and 657 nm, respectively.
As is expected, their spectral tuning effect can still be clearly
observed (Supporting Information Figure S7).
2.3. Photoluminescence Enhancements in QDs by Metal
Nanowire-Loaded AAO Templates
The above results have shown that the AAO templates are
capable of shaping QD light emission spectra. However, the
photoluminescence intensity change is not as significant as
that of the spectral shape, which is due mainly to the weak local
electromagnetic field enhancement induced by the pristine
AAO template. For future photonic applicationsthe ability to
achieve simultaneous spectral shaping as well as large emission
enhancement is strongly needed. AAO has also been known as
an excellent template for the directional growth of ordered functional nanostructure arrays.[57,58] This characteristic provides
an opportunity for constructing multifunctional platforms on
a single substrate. Metallic nanostructures are well known for

their plasmonic resonances that can accelerate various optical

processes through the largely enhanced local optical fields.
Thus it is anticipated that combining the AAO template with
metal nanostructures can simultaneously shape and enhance
the emission of the QDs. We therefore attempted to grow metal
nanostructure arrays using the AAO templates and studied the
effects of the hybrid structures on the photoluminescence properties of the QDs.
In our experiments, Au and Ag nanowire arrays were grown
along the pores of the AAO templates using electrochemical
method (Figure 3a). We choose a specific AAO template with
thickness of 5.2 m in this study. The obtained nanowires
exhibit relatively uniform sizes and shapes. The morphologies
of typical Au nanowires captured after dissolving the template
are shown in Figure 3b. Their diameters are measured to be
22 3 nm, which are restricted by the pores of the template.
The metal nanowires located inside the pores can effectively act
as optical antennas concentrating the incident light and transferring the energy into the FabryProt cavity modes. In this
mannerthe FabryProt resonances of the AAO templates can
couple with the plasmon resonances of the metal nanowires

Figure 3. Photoluminescence of QDs deposited onto metal nanowire-loaded AAO templates. a) Schematic system of an AAO template loaded with
metal nanowires. b) Transmission electron microscopy (TEM) image of typical Au nanowires prepared using the AAO templates. c) Extinction spectra
of the pristine AAO template (green) and hybrid structures with a Ag nanowire array (dark blue) and a Au nanowire array (red) inside the pores of
the AAO templates. The film thicknesses of the AAO templates are 5.2 m. d) Photoluminescence spectra of the QDs deposited onto pristine AAO
template (dark blue), AuAAO (green), and AgAAO hybrid templates (red). e) Comparison of the electric field intensity enhancement distribution
(cross-sectional view) between an AAO template loaded with Au nanowires (left panel) and a pristine AAO template (right panel). The calculation was
carried out at an excitation wavelength of 700 nm with an incidence angle of 26 according to the photoluminescence measurement setup. The hybrid
template is modeled as Au nanowire arrays immersed into a uniform matrix with refractive index of 1.61. The length and diameter of the nanowires
were taken as those from the TEM measurements.

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Figure 4. a) Normalized extinction spectra of the hybrid templates with Ag nanowire arrays inside the pores of the AAO templates. The hybrid
plasmon resonances of the templates locate at 740 nm (dark blue), 780 nm (green), and 805 nm (red). The film thicknesses of the AAO templates are
5.2 m. b) Photoluminescence spectra of the QDs deposited onto the three hybrid templates in (a). The spectra collected for QDs deposited onto
quartz substrate (yellow) and pristine AAO template (purple) are also included for comparison.

and form hybrid plasmonic modes.[59] Such a mechanism

thereafter gives rise to the extinction response of the hybrid
structure, showing broad plasmonic extinction peaks with pronounced spectral oscillations at the long-wavelength edge of the
visible spectrum (Figure 3c). To measure the extinction spectra,
we used a p-polarized light source with an incident angle of 70,
which can simultaneously excite both of the longitudinal and
transverse plasmon modes of the nanowires. The longitudinal
plasmon bands of the Ag and Au nanowire arrays center around
740 nm and 940 nm, respectively, while the transverse plasmon
modes of the hybrid structures are around 400 nm and 510 nm,
respectively. It should be noted that the longitudinal plasmon
modes couple much more strongly with the FabryProt modes
than the transverse ones. This is due to the fact that the Fabry
Prot resonance strengths are weaker in the short-wavelength
range (Figure 1d). Furthermore, in comparison with the pristine AAO template, the hybrid structures show much higher
light extinction due to excitation of the plasmon resonances in
the metal nanowires.
Figure 3d gives the photoluminescence spectra of the QDs
deposited onto the backside of various substrates, including
the pristine AAO template and hybrid AAO templates loaded
with Au and Ag nanowire arrays (referred to as AuAAO and
AgAAO, respectively). Besides shaping the spectral profile,
the hybrid templates can further enhance the emission intensity of the QDs in comparison with the pristine AAO template.
Such enhancements are attributed to the electric field intensity
enhancements induced by the excitation of plasmon resonances
in the metal nanowire arrays. The electric field distribution of
the templates at the excitation wavelength 700 nm was then
calculated to unveil the enhancement mechanism. As shown
in Figure 3e, in comparison with the pristine AAO template,
remarkable electric field intensity enhancements can be seen
near the ends of the nanowire arrays, giving rise to the increase
of the photoluminescence intensity of the adjacent QDs. The
photoluminescence enhancement factors at 790 nm are found
to be 1.9 and 1.6 for AgAAO and AuAAO templates, respectively. The smaller enhancement factor observed for the Au
AAO template is due to the relatively large separation between
its plasmon resonance wavelength (940 nm) and either the excitation wavelength (700 nm) or the emission peak of the QDs

Adv. Optical Mater. 2014, 2, 5664

(790 nm). The plasmon resonance of AgAAO template locates

in-between the excitation and emission wavelengths, thereby
enhancing both the excitation and emission rates of the QDs.
One useful virtue of the hybrid structures is that the longitudinal plasmon bands can be tailored through tuning the length
of the nanowires by controlling the electrochemical deposition
period. In this way, an optimum photoluminescence enhancement can be achieved by carefully choosing a hybrid template
with a plasmon band in resonance with the intrinsic photoluminescence peak of the QDs. Figure 4a renders the normalized
extinction spectra for three AgAAO hybrid templates with their
longitudinal plasmon bands at 740 nm, 780 nm, and 805 nm.
The corresponding photoluminescence spectra for QDs deposited on these three templates are shown in Figure 4b, and are
compared with the spectra collected from the pristine AAO
template and quartz substrate. From Figure 4b one can calculate the photoluminescence intensity enhancement factors via
dividing the emission intensity of QDs deposited onto various
templates by that of the QDs deposited onto the quartz substrate. Table 1 gives the comparison of the photoluminescence
intensity enhancement factors between different templates.
Both of the enhancement factors at the emission peak and integrated in the range from 750 nm to 950 nm were investigated.
It is clearly seen that when the plasmon band (780 nm and
805 nm) is close to the QDs emission wavelength (790 nm),
the photoluminescence spectrum shows the largest intensity enhancements among those from all the four structures.
The enhancement factor at the emission peak of 800 nm can

Table 1. Comparison of the photoluminescence intensity enhancement

factors among different templates.
Templates

Enhancement factor at
800 nm

Integrated enhancement
factora)

QDs-Ag-740

2.1

1.7

QDs-Ag-780

4.2

3.9

QDs-Ag-805

4.9

4.0

Pristine AAO

1.3

a)

The integration range is between 750 nm and 950 nm.

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reach 5 using hybrid Ag-AAO template with plasmon band

at 805 nm. The same structure also exhibits a maximum integrated enhancement factor of 4.0. One can also anticipate that
if the transverse plasmon mode could be tuned to match the
excitation wavelength (700 nm), further intensity enhancements can be achieved, which is beyond the scope of the present work.

3. Conclusion
We have prepared pristine AAO templates with strong Fabry
Prot resonances by a facile and low-cost electrochemical
method. The FabryProt resonances are utilized to shape
the emission spectral profile of the semiconductor QDs. The
underlying mechanism was investigated via transient photoluminescence characterizations and theoretical calculations,
which indicate that tuning of the spectral shape is governed by
the modified PLDOS. The AAO templates have been further
employed to direct the growth of metal nanowire arrays. After
loaded with Au or Ag nanowires, the hybrid templates can further enhance the photoluminescence intensity of the QDs due
to the plasmon-induced electric field intensity enhancements.
We believe that these results can greatly expand the functionalities of the AAO templates and provide a new avenue for
controlling the emission properties of QDs beneficial to the
development of future photonic and optoelectronic applications.

4. Experimental Section
Preparation of the AAO Templates: The AAO templates were prepared
using a two-step anodization process. First, the aluminum sheets
(purity 99.999%) were degreased in acetone and electropolished under
a constant voltage of 16 V for 4 min in a mixture of HClO4 (volume
percentage of 72%) and C2H5OH (volume ratio of 1:3) at 0 C to smooth
the surface morphology. In the first and second anodization processes,
treated aluminum sheets were exposed to a H2SO4 solution (0.3 M) under
constant voltage of 19 V in an electrochemical cell at a temperature of
4 C. The alumina layer produced by the first anodization process was
then removed by wet chemical etching in a mixture of phosphoric acid
(0.15 M) and chromic acid (0.60 M) at 60 C for 1 h. The barrier layer of
AAO templates was thinned by stepwise potential reduced anodization
steps. The final reduced potential was 6 V. The film thicknesses of the
AAO templates were controlled by anodization time. In the final step the
underlying aluminum substrate was dissolved using aqueous CuCl2
(1.5 M) solution.
Growth of the Metal Nanowire Arrays Using AAO Templates: The
metal nanowire arrays were grown in the pores of the AAO templates
by alternative current electrodeposition in an electrolyte. For growth of
the Ag nanowire array the reactants were composed of AgNO3 (0.03 M)
and H2SO4 (0.03 M), while for the Au nanowire array, HAuCl4 (0.01 M)
and H2SO4 (0.1 M) were used. During the electrodeposition a Pt foil
was utilized as counter electrode. After the metal nanowire arrays with
desired lengths were obtained the underlying aluminum substrate was
dissolved using aqueous CuCl2 solution (1.5 M).
Instrumentation: The extinction spectra were measured on a
PerkinElmer Lamda 950 UV-visible-NIR spectrophotometer. TEM
imaging was performed on a JEOL 2010HT microscope at 100 kV. For
preparation of the TEM samples, the AAO matrixes were removed by
dissolving the templates containing metal nanowires in aqueous NaOH
solution (1.25 M). SEM imaging was conducted on a Zeiss Auriga-3934
microscope operating at 20.0 kV.

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The photoluminescence measurements were conducted in reflection

mode. In a specific measurement, a p-polarized laser beam was
generated by a mode lock Ti:Sapphire laser (MaiTai, Spectra Physics)
with a pulse width of 150 fs and a repetition rate of 79 MHz. The
excitation wavelength was tuned to 700 nm and the power is 5 mW
measured at the samples. The scattering noise was filtered by a band
pass filter. A 100 mm-focal-length lens was used to excite the sample
at a Brewster angle of 50. The photoluminescence from the sample
was collected using a focusing lens, and transmitted through a longwave pass filter before entering the liquid-nitrogen-cooled CCD (SPEC10, Princeton). For measuring the photoluminescence of the QDs with
intrinsic emission peak at 607 nm and 657 nm, we use two-photon
photoluminescence technique and the excitation wavelength was tuned
to 800 nm with a power of 30 mW. Time-resolved photoluminescence
decay traces were recorded using a time-correlated single-photon
counting system (PicoQuant GmbH).
Numerical Calculations: Numerical simulations of the dipole
emission spectrum, the total decay rate, and the electric field intensity
enhancement contours were conducted using finite-difference timedomain (FDTD) method (FDTD Solutions 8.0, Lumerical Solutions,
Inc.). The AAO template was modeled as a periodic structure with
a unit cell as indicated in Figure 2b, i.e., ordered air pores inside a
dielectric matrix with refractive index of 1.61. According to the SEM
measurements, the diameter of the air pore was set as 22 nm. A mesh
size of 1 nm was used for meshing the air pores and larger mesh sizes
were used for other homogeneous areas. In all the calculations we used
periodic boundary conditions in the xy plane while perfectly matched
layers (PMLs) were adopted in the z direction. For calculations of
the emission profile and the total decay rate, the radiative source is
treated as an oscillating classical point dipole placed at 10 nm above
the AAO template. The dipole source has an emission spectrum with
a Lorentzian-shape profile, peaked at 790 nm and ranged from 600 to
1000 nm. In the FDTD calculations, the far-field radiation power from
the dipole source was collected by integrating the Poynting vector over
a surface (with an area equal to the unit cell) placed at 900 nm above
the AAO template while the total radiation power from the dipole was
collected by integrating the Poynting vector over the six surfaces of
an enclosed cube (with each surface 8 nm to the center of the dipole)
surrounding the dipole. The ratio between the total power radiated from
the dipole on the AAO template and that from the dipole in free space is
defined as the relative total decay rate.
For calculations of the electric field intensity enhancement
distribution in the pristine AAO template and the one loaded with Au
nanowire arrays, a buffer layer of 10-nm thick alumina oxide was added
at the backside of the template.[60,61] The complex dielectric constants
of Au were taken from the reported values.[62] The excitation light is
p-polarized and the incidence angle is 26 by taking into account of the
refractive index difference between the alumina oxide and air.
Calculations of the PLDOS: The PLDOS above the AAO template was
calculated using the Green function method, and the PLDOS is given
as[56]


D (r , T) =




2T
 
Im Tr G (r , r , T)
Bc 2

(4)

where Im stands for the imaginary part and Tr denotes the trace
of the Green tensor matrix in brackets. The Green tensor can be
obtained as




 



E r , T = iT: 0 G r , r , T j T

(5)

In our calculations we used an electric dipole to model the point

source and once the electric field at the position of the dipole is given,
the Green tensor can thereafter be computed. The numerical calculations
were conducted using finite element method (COMSOL v4.2a). The
hexagonal air hole lattice in the AAO template is simulated with 11 11
arrays. Perfectly matched layers were used for the boundary conditions.
The thickness of the template was set to 5.2 m, and the refractive

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Optical Mater. 2014, 2, 5664

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Supporting Information
Supporting Information including SEM images of the AAO templates
with various film thicknesses and the corresponding transmission
spectra, SEM image of QDs dispersed on Si substrate and the backside
of the AAO template, photoluminescence spectra of the QDs deposited
on the AAO templates with various thicknesses, spectral shaping effects
of the QDs with different sizes, and calculated PLDOS at the backside
of the AAO templates is available from the Wiley Online Library or from
the author.

Acknowledgements
Z.-K. Zhou, D. Y. Lei, and J. M. Liu contributed equally to this work.
This work was financially supported by the National Basic Research
Program of China (Grant No. 2010CB923200), the National Natural
Science Foundation of China (Grant Nos. U0934002, 20828001,
11204385, 51202300), the Ministry of Education of China (Grant No.
V200801), the Doctoral Fund of Ministry of Education of China (Grant
No. 20120171120012), the Natural Science Foundation of Guangdong
Province (Grant No. S2012040007814), the Fundamental Research Funds
for the Central Universities (Grant No. 12lgpy45), and Fund of Education
Department of Guangdong Province (Grant No. 2012LYM_0011). D. Y. L.
and X. L. acknowledge the grants 1-ZVAW and 1-ZVAL administrated by
the Hong Kong Polytechnic University. Zhang-Kai Zhou, Dang Yuan Lei,
and Jiaming Liu contributed equally to this work.
Received: August 20, 2013
Revised: October 13, 2013
Published online: November 13, 2013

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