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Controlled coupling of a single nanoparticle in polymeric microstructure by low one-photon

absorption—based direct laser writing technique

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 Nanotechnology

Nanotechnology 26 (2015) 105301 (8pp) doi:10.1088/0957-4484/26/10/105301

Controlled coupling of a single nanoparticle

in polymeric microstructure by low one-
photon absorption—based direct laser
writing technique
M T Do, D T T Nguyen, H M Ngo, I Ledoux-Rak and N D Lai
Laboratoire de Photonique Quantique et Moléculaire, UMR 8537 CNRS, Institut d’Alembert, École
Normale Supérieure de Cachan, 61 avenue du Président Wilson, F-94235 Cachan cedex, France

E-mail: nlai@lpqm.ens-cachan.fr

Received 15 December 2014, revised 15 January 2015

Accepted for publication 26 January 2015
Published 20 February 2015

Abstract
We investigated the coupling of a single nanoparticle (NP) into a polymer-based photonic
structure (PS). The low one-photon absorption microscopy with a two-step technique allowed us
first to accurately determine the location of a NP and then to embed it as desired into an arbitrary
PS. The coupling of a gold NP and a polymer-based PS was experimentally investigated
showing a six-fold photon collection enhancement as compared to that of a NP in unpatterned
film. The simulation results based on finite-difference time-domain calculation method
confirmed this observation and showed a 2.86-fold enhancement in extraction efficiency thanks
to the NP/PS coupling.
Keywords: direct laser writing, ultralow one-photon absorption, photonic coupling, gold
nanoparticle
(Some figures may appear in colour only in the online journal)

1. Introduction demonstrate that by using a simple fabrication technique

Recently, the concept of a photonic structure (PS) containing
active molecules or fluorescent nano-objects has drawn a
great attention due to their wide range of applications. Many
kinds of nanoparticles (NPs) have been investigated and
coupled to host PSs, for instance, self-assembled quantum
dots embedded in a distributed Bragg reflector cavity struc-
ture [1], or a nitrogen-vacancy color center in diamond
incorporated with different kinds of structures like optical
fiber for quantum information application [2] or resonators
[3, 4], or a gold NP coupled with a cavity system [5].
Although PS/NP coupling has been intensively investigated
both theoretically and experimentally, the fabrication of such
a kind of functionalized nano- or micro-structures still
remains a great challenge since most PS/NP coupled struc-
tures require complicated and expensive techniques.
In this article, we report our investigation of the coupling
of a single NP with a polymer-based PS. First, we
called low one-photon absorption direct laser writing (LOPA
DLW) [6, 7] with a double step process, it is possible to
address most kinds of NPs and to precisely embed them into
desired polymeric PSs. Then, we show theoretically and
experimentally how this PS/NP coupling strongly enhances
the fluorescence of the embedded NP.
2. Experimental setup
LOPA DLW consists of a combination of an ultralow
absorption photoresist and a high focusing regime [6],
allowing the fabrication of two- and three-dimensional
(2D, 3D) structures with submicrometer resolution [7],
opening the way to many promising applications [8]. Our
technique requires only a continuous-wave laser as the
excitation source for the whole fabrication process. This is
an advantage over DLW technique using the two-photon

0957-4484/15/105301+08$33.00 1 © 2015 IOP Publishing Ltd Printed in the UK

Nanotechnology 26 (2015) 105301 M T Do et al

Figure 1. (a) Sketch of the experimental setup of the LOPA-based direct laser writing technique. M: mirror; S: electric shutter; P: polarizer; λ/
2, λ/4: half-wave plate and quarter-wave plate, respectively; PZT: piezoelectric translation stage; DM: dichroic mirror; F: 580 nm long-pass
filter; Ph: pinhole (diameter = 100 μm); L1, L2: lenses; APD: avalanche photodiode. (b) Measured UV-visible absorption spectra of SU8
photoresist (top) and of 50 nm-diameter spherical gold nanoparticles in water (bottom). The vertical line denotes the excitation wavelength of
532 nm.

absorption mechanism [3], which requires an expensive
and complex femtosecond pulsed laser source. The LOPA
experimental set-up is sketched in figure 1(a). For PS
fabrication, we used a negative tone SU8 photoresist
(MicroChem Corp.). Gold NPs (50 nm—diameter, in water
solution, Sigma-Aldrich) were chosen, as example of
active NPs to be coupled into SU8 PSs. The sample con-
sisting in a thin monolayer of Au NPs sandwiched between
two SU8 layers was prepared by spin-coating. First, a layer
of SU8 2000,5 was spin-coated on a cleaned cover glass.
Second, 50 μL of a diluted and perfectly dispersed Au NPs
solution was spin-coated on the surface of the first layer.
Then, the second layer of SU8 2000,5 was spin-coated on
top of the Au NPs layer. Note that, after each step, the
sample was soft-baked on a hot plate at 65 °C (3 min) and
95 °C (5 min) to remove the residual solvents. A total film
thickness of around 1.0 μm and a smooth surface profile
were subsequently confirmed by a profilometer. The
sample was mounted on a 3D piezoelectric actuator stage
(PZT). A high numerical aperture oil-immersion objective
(Fluar × 100/1.3 NA, Zeiss) placed beneath the glass
coverslip was used to focus the excitation laser beam. A
continuous wave laser operating at 532 nm (Oxxius) was
used for both mapping and fabrication processes. The
fluorescence signal emitted by Au NPs was collected by
the same objective, filtered by a 580 nm long-pass filter to
eliminate the excitation light, and detected by an ava-
lanche photodiode.
3. Fabrication
The first step of the fabrication process consists in localizing
the Au NPs embedded between two SU8 layers. We note that
Au NPs emit fluorescence in the visible range when excited
by UV or visible (plasmonic resonance) light (see figure A1
in appendix). Fluorescence images of Au NPs were obtained
by raster scanning the sample through the focusing spot.
According to the high absorption of Au NPs at the used
wavelength (figure 1(b)), a very low excitation power (less
than 0.1 mW, or less than 0.0022 W μm−2 at focusing region)
was employed. This power is weak enough not to induce any
polymerization of the SU8 photoresist, then no structure is
formed during the mapping process. First, a large area
(100 × 100 (μm2)) of the sample was scanned and many
individual Au NPs were found (see figure A2 in appendix).
We then pointed out the position of each NP by scanning a
small area of 2 × 2 (μm2) around the NP, in the (xy)-and (xz)-
planes, respectively, as shown in figure 2(a). We achieved a
lateral resolution of about 243 nm (figure 2(b)), and an axial
resolution of 730 nm (figure 2(c)), which actually corresponds
to the diffraction limit of the used objective lens. The curve
plotted in figure 2(d) is an extract of data corresponding to a

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Nanotechnology 26 (2015) 105301
Figure 2. (a) Illustration of a sample area in which a gold NP is sandwiched in between SU8 films. Fluorescence scanning is achieved in the
(xy)-and (xz)-planes, as indicated by the red border rectangles. (b) and (c) fluorescence images obtained by scanning along the (xz)-and (xy)-
planes, respectively. (d) Extract of data corresponds to the dotted line shown in (c) showing the fluorescence intensity as a function of the NP
position and of the precision of its position determination.
scan along the dotted line passing by the center of the NP
(figure 2(c)), showing the fluorescence intensity as a function
of position. The sharp peak reveals a precision <20 nm for the
position determination.
Once the position of a single NP is determined, the
fabrication of PSs containing this NP will be realized. For the
fabrication step, the excitation power was increased due to the
ultralow absorption of SU8 photoresist at 532 nm excitation
wavelength [7]. In this work, we have chosen a power of
3.8mW (0.084 W μm−2 at focusing region) for all fabrica-
tions. The target structure is made of micropillars arranged in
a hexagonal 2D photonic crystal. The NP was chosen to be
located at the central pillar of the hexagonal structure. The
fabrication of each pillar was realized by scanning the
focusing spot (scanning speed = 1 μm s−1) along the vertical
direction (z-axis) and through the total SU8 film thickness
(total moving distance of 2 μm). In this work, we did not aim
at investigating the effect of the periodic microstructure, so
the geometric parameters of the micropillars pattern were
chosen to keep the photonic bandgap (if any) of the micro-
pillars hexagonal structure remote from the emission band of
the Au NP embedded inside the structure. The micropillar
pattern was made here only to ensure the accurate localization
of NPs by identifying the pillar containing the single Au NP.
After the exposure step, the sample was post-baked on a hot
plate at 65 °C (3 min) and 95 °C (5 min) to finalize the cross-
3
M T Do et al
linking process, followed by the development step. The pat-
terned sample was then placed again on the PZT stage, at the
same position as in the fabrication step, in order to perform
optical characterization and comparison. The morphology and
surface topography of each structure was subsequently
examined by optical microscopy and scanning electron
microscopy (SEM). Figure 3(a) shows a SEM image of 10
hexagonal structures, each of them containing a single Au NP
at its center. We expected to obtain a micropillar containing a
single Au NP. Surprisingly, a microsphere was formed at the
position of the Au NP instead of a micropillar. In this image,
all micropillars patterns have the same parameters (center-to-
center distance of 1.50 μm, diameter of each pillar of about
0.32 μm and the height of a pillar = 1.00 μm), the micro-
spheres at the center display different diameters varying from
0.76 to 1.40 μm. Figures 3(b) and (c) show SEM images of a
hexagonal structure, in which a quasi-sphere with a diameter
of 1.12 μm and containing a single Au NP was obtained at the
structure center.
The formation of the microsphere can be explained by a
thermodynamic model shown in figure 3(d). During the
continuous irradiation by the focused laser beam, Au NP
strongly absorbs green light (see figure 1(b)) due to the
strongly localized surface plasmon resonance. The absorp-
tion energy decays mainly non-radiatively via electron–
phonon collisions followed by phonon–phonon relaxation.
Nanotechnology 26 (2015) 105301 M T Do et al

Figure 3. (a) SEM image of different fabricated structures, each of them containing a single gold NP at the center. (b) SEM image of an
individual structure corresponding to number 5 in (a). (c) Zoom in of the center of the structure. (d) Thermodynamic model used to explain
the formation of the spherical structure containing a gold NP. The two-ends arrows passing by the NP denote the heat diffusion from NP,
which originates the thermopolymerization effect around the NP.

As a result, the NP is continuously heated and radially dif-
fuses heat beyond its surface to the surrounding medium
[9, 10]. Meanwhile, SU8 photoinitiators within the focal
spot absorb one-photon energies from the incident light to
generate a certain number of strong acids (Lewis acid). The
AuNP at that time plays the role as a ‘hot spot’: in the
vicinity of the Au NP, the temperature is noticeably
increased, then accelerate the generation rate of acids. Since
heat is diffused according to a spherical symmetry, the
polymerization rate of SU8 is much higher in a sphere
centered on Au NP. As long as the temperature is high
enough (>75) °C, the SU8 polymer chains are continuously
formed [11]. As a result, a spherical structure of a poly-
merized photoresist was obtained during the fabrication
process. The amount of heat generated by the plasmonic NP
can be controlled by the particle size and shape, as well as
illumination strength, wavelength and irradiation duration.
Hence the interplay of the AuNP with the excitation light
allows the spatial and temporal heat management leading to
controllable fabrication processes. With this given experi-
mental setup, there are two possible ways for controlling the
sphere size: either by excitation intensity or by exposure
time. It is worth to mention that the formation could be out
of control if light intensity is too high, because the tem-
perature at the Au NP position can exceed either its defor-
mation point (such as melting point, fragmentation
threshold) [10] or the boiling point of the host SU8 material.
In such a case, heat storage may result in a micro-explosion.
In this work, fabrication parameters were the same for all
structures and weaker than those of damage threshold, but
the microsphere diameter varied from 0.76 to 1.40 μm due to
the variation of the Au NPs size. It is important to mention
that the microsphere is not the PS that we intended to fab-
ricate. However, as it will be shown later, such a photonic
microsphere could be a valuable PS for the enhancement of
NP optical properties. In general case, when working with
NPs without thermal effects, such as diamond NP, nonlinear
NP, etc, this very simple LOPA-based two-step technique

4
Nanotechnology 26 (2015) 105301
Figure 4. Fluorescence images of fabricated structures obtained in (xy)-plane (a), (c) and in (xz)-plane (b). (c) Image of the microsphere
containing a single Au NP. (d) Comparison of fluorescence signals in two cases, Au NP in a microsphere (blue curve) and in an unpatterned
SU8 photoresist film (red curve).
should allow to fabricate structures as desired, including
microspheres.
4. Characterization: fluorescence measurement
Figure 4 shows the fluorescence images of the fabricated
structures, using the same excitation power as in the mapping
step. It is obvious that the emission spot at the structure center
is very bright as compared to the weak emission of the sur-
rounding micropillars (figures 4(a) and (b)). Note that SU8
micropillars also emit fluorescence, but with very low rate.
Figure 4(c) shows a zoom on the fluorescence image of the
microsphere only. This clearly confirms the existence of a
single Au NP inside the microsphere. Furthermore, by com-
paring the fluorescence signal obtained before fabrication (Au
NP embedded in SU8 films) and after fabrication (Au NP
embedded in a microsphere), we found a strong enhancement.
The red and blue curves in figure 4(d) represent the fluores-
cence intensity of the same Au NP, obtained before and after
fabrication, respectively. For a sphere with a diameter of
1.12 μm (figure 3(b)), we estimated a six-fold enhancement of
the collected fluorescence rate. For all other structures, the
enhancement factor varies between 3.0-fold and 6.0-fold, due
the difference of the microspheres sizes.
The origins of the fluorescence enhancement can be
attributed to: (i) geometric modification of the fluorescence
pattern thanks to the microstructure and (ii) the change of
fluorescence emission signal when the surrounding medium
of Au NP varies (SU8 changes from non-polymerized to
polymerized states). We expect the first reason to play a
5
M T Do et al
dominant role, since the optical properties of SU8 do not
change significantly between the two states. Actually, a
similar structure, called solid immersion lens [12], allowing to
enhance the fluorescence emission of a single emitter has
been also reported.
5. Numerical simulation
In order to understand the fluorescence enhancement in the
case of NP/PS coupling, we performed a finite-difference
time-domain (FDTD) simulation using a commercial
‘Lumerical’ software. Because the emission from a small
isolated spherical Au NP depends on the excitation field, the
Au NP can be modeled as a single oscillating electric dipole
[13, 14], whose orientation is parallel to the interface between
SU8 and glass substrate, corresponding to the excitation
polarization at the focusing spot. We assumed that the single
dipole emits at λ = 650 nm, which is arbitrarily chosen within
the fluorescence spectrum of Au NPs (see figure A1 in
appendix). This wavelength does not correspond to the
maximum fluorescence spectrum, but it does not affect the
generality of the calculation method. For simulations, we
considered two particular configurations: a single Au NP
embedded in a SU8 film (F configuration) and a single Au NP
embedded in a SU8 microsphere (S configuration). For both
cases, we assumed that the oscillating dipole is located in SU8
photoresist at d = 500 nm from the interface between SU8 and
glass substrate and the detector is located at the objective lens
position (figure 3(d)). There are different important para-
meters influencing the optical properties of this NP/PS
Nanotechnology 26 (2015) 105301
Figure 5. Calculation of fluorescence extraction efficiency in two situations: a single Au NP in a photoresist microsphere (red curves) and a
single Au NP in unpatterned SU8 photoresist film (blue curves). Simulations are based on FDTD method, with (see figure 3(d)): d = 503 nm,
r = 553 nm, emitted wavelength λ = 650 nm. We also assumed that a single NP corresponds to an absorption/emission dipole oriented parallel
to the air/glass interface. (a) Extraction efficiency versus half θ-angle. (b) Polar diagrams of normalized electric field intensity in (xz)-plane
shows the spatial distribution of the emitted light (radiation pattern).
coupling system, but we focused only on the ‘extraction
efficiency’, which is defined as the ratio of the collected
power to the total power radiated by the electric dipole [15].
We note that the microscope objective is characterized by its
numerical aperture NA = n sin θ , where n is the refractive
index of the immersion medium and θ is the half aperture
angle.
Figure 5(a) shows simulation results of the extraction
efficiency as a function of the θ-angle for both S (red curve)
and F (blue curve) configurations. It can be seen that, with
NA = 1.3, while only ≃22% of the radiated power was
obtained for the case of NP in a SU8 film, ≃63% of the
radiated power can be collected by the NP/microsphere cou-
pling, resulting in a 2.86-fold enhancement in the extraction
efficiency. To explain these simulation results, we note that
for small particles behaving like dipoles close to a dielectric
interface, the radiated power is principally emitted towards
the denser medium at the critical angle [16]. Because a SU8
film possesses a high refractive index n SU8 ≃ 1.6 with respect
to that of glass substrate (n glass = 1.518), the emission from
the AuNP suffered a total internal reflection (TIR) effect, so
that all the emitted light at angles larger than the critical angle
are completely reflected. In contrast, in the case of a Au NP
embedded in a SU8 microsphere, the Au NP is bounded by a
small SU8 volume, surrounded by air, resulting in a low
effective refractive index, as compared to that of glass sub-
strate. Therefore there is no limitation caused by the TIR
effect, then the radiated light is transmitted into the glass
substrate and most of it is collected by the objective. This is
confirmed by the radiation pattern, i.e., the electric field
intensity distribution in the (xz)-plane, shown in figure 5(b). A
single dipole, oriented parallely to the dielectric interface,
emits light mainly in the direction close to the critical angle,
represented by two lobes. We can see that in the case of a S
configuration (red), a significant portion of the emitted light is
located in the vicinity of θc ≃ arcsin(1 n glass ) = 41.2°, which
6
M T Do et al
belongs to the collection cone of the microscope objective,
and could be detected. On the contrary, the radiation pattern
of the F configuration (blue) is oriented at a larger angle and
the radiation intensity is three times weaker, leading to a loss
of photons propagating out of the collection cone of the
microscope objective. Certainly, we cannot directly compare
the experimental results with the numerical calculations
because we have simplified the coupling by considering a Au
NP (50 nm) as a single electric dipole. A complete model and
full mathematical calculation may be necessary for future
complete investigation of such NP/PS coupling.
Beyond the plasmonic NPs used in this work, our tech-
nique can be applied for a wide range of single solid-state
NPs, such as diamond NP containing a single emitter, non-
linear NPs, etc. The LOPA-based direct laser writing could
allow to fabricate other 2D and 3D PSs, which are very
promising for controlling and manipulation of emission
photons.
6. Conclusions
In conclusion, we have demonstrated a simple and low-cost
technique to precisely position and embed a single Au NP
into a photonic microstructure. The coupled NP/photonic
microstructure was realized by a confocal system working in
a very low linear absorption regime, and with a double-step
process: ultralow excitation power for determination of NP
position, and low excitation power for the fabrication of
desired microstructures. The coupling of NP to the micro-
sphere allowed a great enhancement, up to six-fold, of the
extraction efficiency of its fluorescence, as compared to the
case without coupling. Simulations based on FDTD method
confirmed the experimental observation, showing a 2.86-fold
enhancement. This LOPA-based direct laser writing with a
double-step process is very simple but powerful as compared
Nanotechnology 26 (2015) 105301
Figure A1. (a) Absorption spectrum of the used Au NPs. It can be
seen that Au NPs absorb most light in UV range, and also around
532 nm, due to the plasmonic resonance. Fluorescence spectra of the
same Au NPs, obtained by an excitation light at 355 nm (b) and at
532 nm (c). The fluorescence measurement was realized by exciting
the Au NPs in water solution, and detected by an Ocean Optics
spectrometer.
with other complicated and expensive techniques [2, 4, 5, 12].
It is also very promising to embed other NPs, such as dia-
mond NPs containing a single emitter, into desired polymer-
based PSs, thus allowing the manipulation of single photon
emission [4].
Acknowledgments
The authors acknowledge the financial support from the
Labex NanoSaclay in the frame of ONE-FAB-3D and
7
M T Do et al
Figure A2. Fluorescence image of gold nanoparticles. (a) Mapping in
(xy)-plane for a large area of 100 × 100 (μm2). The yellow crosses
indicate the position of single Au NPs, and are numbered from 1 to
11. The light blue dots are not Au NPs but the signals errors, from
electrical noise, during scanning. The Au NPs, which are selected to
fabricate structures, were scanned again individually to determine
precisely their positions.
COGONA projects. MT Do and DTT Nguyen contributed
equally to this work.
Appendix
Figure A1 shows both absorption and fluorescence spectra of
gold NPs in water solution, respectively. The absorption in
UV range is due to the absorption property of gold material
while the strong absorption peak at around 532 nm is due to
plasmonic resonance of 50 nm-diameter gold NPs. When
excitating by either 355 nm or 532 nm laser beam, gold NPs
emit fluorescence as indicated by figures A1(b) and (c),
respectively.
Figure A2 shows the fluorescence image of gold NPs that
are sandwiched in between two SU8 thin layers. The gold
NPs were excited by a green laser with very weak power. The
image was obtained by scanning the focusing point of the
LOPA system in (xy)-plane for a large area of
100 × 100 (μm2). Many NPs have been found. The ones,
which are selected to fabricate structures, were scanned again
individually to determine precisely their positions.
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