Hongshi Chen 2022TROY0007

Thèse
de doctorat
de l’UTT
Hongshi CHEN
Contribution to Active Probe

for SNOM and Nanoscale Light-matter
Interaction based
on Photopolymerization
Champ disciplinaire :
Sciences pour l’Ingénieur
2022TROY0007 Année 2022

THESE
pour l’obtention du grade de
DOCTEUR
de l’UNIVERSITE DE TECHNOLOGIE DE TROYES
en SCIENCES POUR L’INGENIEUR
Spécialité : MATERIAUX, MECANIQUE, OPTIQUE ET NANOTECHNOLOGIE
présentée et soutenue par
Hongshi CHEN
le 1er juin 2022
Contribution to Active Probe for SNOM and Nanoscale

Light-matter Interaction based on Photopolymerization
JURY
M. Régis BARILLÉ PROFESSEUR DES UNIVERSTES Président (Rapporteur)

M. Thierry GROSJEAN DIRECTEUR DE RECHERCHE CNRS Rapporteur
M. Tao XU ASSOCIATE PROFESSOR Examinateur
Mme Shuwen ZENG CHARGEE DE RECHERCHE CNRS Examinatrice
M. Renaud BACHELOT PROFESSEUR DES UNIVERSTES Directeur de thèse
M. Jérôme PLAIN PROFESSEUR DES UNIVERSTES Directeur de thèse
Contents
Abstract ................................................................................................................................ 3
Chapter 1 Introduction and Context .................................................................................... 4
1.1 Scanning near-field optical microscopy: attempt to breaking diffraction limit ........ 4
1.1.1 SNOM principles .......................................................................................... 6
1.1.2 Information transfer from near-field to far-field ............................................ 8
1.2 Light-matter interaction between metallic nanostructure and nano-emitter......... 12
1.2.1 Surface plasmons ...................................................................................... 12
1.2.2 Metal enhanced fluorescence .................................................................... 14
1.3 Summary .............................................................................................................. 15
References ................................................................................................................. 17
Chapter 2 Photopolymerization for polymer probe ............................................................ 22
2.1 Photopolymerization reaction ............................................................................... 22
2.1.1 Formulation composition ............................................................................ 23
2.1.2 Polymer stiffness ........................................................................................ 24
2.2 Approach of Fabrication of polymer tip on the surface of cleaved fiber end........ 26
2.2.1 FDTD simulation for photopolymerization on fiber end ............................. 26
2.2.2 Procedure of Fabrication polymer probe on fiber end ............................... 29
2.3 Polymer tip used as a scanning probe ................................................................. 36
2.3.1 Principles of the shear force regulation ..................................................... 37
2.3.2 Effect of the probe compliance .................................................................. 43
2.4 Summary .............................................................................................................. 45
Reference ................................................................................................................... 46
Chapter 3 Attachment of few fluorescence emitters on polymer at different scales ......... 49
3.1 Optical system ...................................................................................................... 49
3.1.1 High resolution confocal observation system ............................................ 50
3.1.2 Time-resolved Photoluminescence measurement ..................................... 51
3.2 Attachment of single emitter from glass substrate ............................................... 54
3.3 Attachment of emitters on an extra tip obtained by second exposure on polymer
probe........................................................................................................................... 61
3.4 Hybrid nano-emitters based on the local intergration of quantum nano-emitters to
vicinity of plasmonic nano-structures ......................................................................... 65
3.4.1 Principle...................................................................................................... 65
3.4.2 Attachment of fluorescence polystyrene nanospheres on gold nanocube 68
3.4.3 Integration of QDs to the vicinity of nanocube ........................................... 71
3.5 Summary .............................................................................................................. 75
Reference ................................................................................................................... 76
Chapter 4 Investigating nanostructures by using new polymer probe .............................. 79
4.1 Scanning on silver nanowires by using bare polymer probe ............................... 79
4.1.1 Sample preparation .................................................................................... 79
4.1.2 Observing surface plasmon by probe ........................................................ 81
4.2 Scanning on gold nanocube by using active probe ............................................. 86
4.2.1 Characterization of nanocube and active probe ........................................ 87
1
4.2.2 Fluorescence imaging with excitation from bottom and sample scanning 90
4.2.3 Lifetime measurement when active probe scanning on single nanocube. 95
4.3 Summary .............................................................................................................. 97
Reference ................................................................................................................... 98
Conclusion ....................................................................................................................... 100
Annex ................................................................................................................................... 1
Résumé en Français............................................................................................................ 1
1 Introduction ................................................................................................................ 1
2 Photopolymérisation pour sonde polymère ............................................................... 2
2.1 Méthode de fabrication d'une pointe polymère sur la surface d'une extrémité
de fibre................................................................................................................... 2
2.2 Pointe polymère utilisée comme sonde de balayage ..................................... 8
3 Attachement de quelques émetteurs de fluorescence sur sonde polymère ........... 11
3.1 Attachement d'un seul émetteur à partir d'un substrat en verre ................... 11
3.2 Plasmon-émetteur hybride en intégrant des nano-émetteurs au voisinage de
la nanostructure plasmonique ............................................................................. 18
4 Étude des nanostructures avec la nouvelle sonde polymère ................................. 26
4.1 Balayage sur la surface de nanofil d'argent avec une sonde polymère ....... 26
4.2 Balayage de nanocube d'or en utilisant une sonde active ........................... 29
Reference ................................................................................................................... 36
2
Abstract
Scanning Near-field Optical Microscope (SNOM) is a technology for high

resolution optical imaging. The high spatial frequency information from the
near-field is associated to high spatial resolution, allowing one to break the
diffraction limit.
The used local probe is still key topical issue that has been addressed for long.
The thesis deals with the development of an active near-field probe based on
a polymer tip integrated at the extremity of an optical fiber. We polymerized
polymer tip on the surface of the fiber end as a scanning optical probe. Shear-
force method with micro tuning fork is used for controlling the probe-sample
distance.
Chapter 1 is a detailed introduction that presents the framework and remind

principles in nano-optics. The fabrication and use of the polymer probe as a
shear force near-field probe are described in Chapter 2.
After surface functionalization of the polymer probe, a few nano-emitters have
been attached on the probe extremity, to obtain an active probe. Upon
excitation, the nano-emitters can act as local light source for the active probe.
The strategy of attachment and manufacture are discussed in Chapter 3.
Besides, while the development of such active hybrid probes turned out to be
challenging, the developed strategy of attachment has been used on gold
nanocubes on substrate, to create polarization-sensitive hybrid plasmon nano-
emitters. We also extended this hybrid nano-emitters to single photon regime.
Finally, in Chapter 4, the active probe was tested on two kinds of samples: silver
nanowires and gold nanocubes. By using our new active probe, we observed
near-field information for those nanostructures and broke the diffraction limit.
3
Chapter 1 Introduction and Context
1.1 Scanning near-field optical microscopy: attempt to breaking
diffraction limit
In traditional far-field optical imaging, the spatial resolution is limited by the

diffraction limit [1][2]. The idea of Scanning Near-field Optical Microscopy
(SNOM) is to break the diffraction limit by near-field imaging, in the other words,
by studying the near-field information which
decaying evanescent fields [3-5].
In 1928, E.H. Synge first proposed the idea of using a small hole scanning
above the surface of object and detecting the near-field to obtain higher optical
resolution. Because of experiment difficulties, this idea was not realize until
1972, people performed first near-field experimental demonstration at the
microwave domain [7]. In 1982, the group of Dieter Pohl first showed practical
possibility of experiments with visible light [8]. In 1986, Photon Scanning
Tunneling Microscope [9] and Scanning Tunneling Optical Microscope [10]
were developed, both based on frustrated total internal reflection. Thanks to
progress of probe-simple distance control technique and probe fabrication
process, SNOM then developed rapidly in the 1990s [11-16]. Though today
Atomic Force Microscopy (AFM) and Scanning Electronic Microscopy (SEM)
have been standard tools in microscopy for local characterizations, researchers
are still interested about using SNOM for imaging plasmonic nanostructures
[17][18] or biological samples [19][20]. Nearly two decades ago, new SNOM
probe based on optical antennas was proposed [21-23], as well as the idea of
active SNOM probe [24].
For usual SNOM, the probe is a sub-wavelength hole at the apex of a tip
scanning above the sample while maintaining probe-sample distance of a few
nanometers. Therefore, a typical SNOM system is a combination of both optical
microscopy and Scanning Probe Microscopy (SPM). Researchers often use
tapered optical fiber [25] or nano metal tip [26-28] as probes for SNOM. The
SPM system promises the probe operating in sub-wavelength near-field zone,
since the evanescent waves decay exponentially. To control probe-sample
distance people developed several implementations for different probes, for
example, tuning fork shear (lateral) force [11][12] or normal force (tapping)
[13][14] method for fiber probes, bent-fiber probes work as AFM cantilever
[29][30], standard AFM cantilever with a hole in the center of its pyramidal tip
[31], tunneling current feedback with metal tip [15][16]. Though the complexity
of the systems leads experimental difficulties and slow speed of recording,
researchers can obtain the topographical and optical information
4
simultaneously and correlate the two with sub-wavelength precisions.
In this thesis, we have worked on the development of a new active SNOM probe
based on polymer tips and nanoemitters. The probe is photopolymerized on the
fiber end and is compatible with the tuning fork shear force method to control
probe-sample distance. We will see that, compared to traditional non metallized
tapered optical fiber made by pulling or etching techniques, probe made by
photopolymerization has a better field confinement because the light-induced
polymer tip is a reproduction of propagating field [32]. In the other hand, the
stiffness of polymer is quite smaller than silica (used for optical fiber) or metal,
which constituts a big challenge of probe-sample distance control. Details will
be further discussed at Chapter 2.
For getting a light-emitting probe, we have used nanoemitters (Quantum Dots,
According to the Bethe-Bouwkamp-Theory, emission of a small aperture is

equivalent to an electric and magnetic dipole located at the position of the
aperture [33]. Thus, alternatively, nanoemitters may act as local emitters to
accomplish local scattering for information transfer from near-field to far-field.
The fluorescent signal can be filtered from large excitation signal by using a
bandpass filter. Instead of aperture size, the size of nanoemitter defines the
highest spatial frequency of detectable signal. In the case of aperture probes,
as metal-coated dielectrics waveguides, low light throughput is the price to pay
for their superior light confinement. Even worse, for such aperture probe, about
two thirds of incoming energy will be absorbed by metal layer, which results in
considerable heating of its metal coating, which finally get damaged [34]. For
nanoemitters used for active probe, the fluorescent field confinement only
depends on the size of emitter, due to lack of metal layer, there is need to worry
about heating problem, only the properties of nanoemitter itself may limit its
throughput, for example, strong excitation light could lead to the bleaching of
nanoemitters [33]. Meanwhile, the involvement of nanoemitter makes the probe
fabrication process a challenging task: strategies of location and fixing of the
nanoemitter have to be studied, and this point will be discussed in Chapter 3.
In Chapter 3 and Chapter 4, we will report on the use of this active probe to
study plasmonic nanostructures: silver nanowires [37] and gold nanocubes [38]
are tested and analyzed. Plasmonic nanostructures may have good light fields
confinement at its vicinity, leads to a strong near-field signal. For nanowire,
propagating surface plasmon polariton (SPP) along the wire is observed. For
nanocube, near-field fluorescence enhancement cause by localized surface
plasmon resonance (LSPR) is detected.
Moreover, in Chapter 3, taking advantage of the acquired experience, methods
and materials, we have used the LSPR of gold nanocubes for locally triggering
photopolymerization, resulting in hybrid plasmon-emitter system [39]. When we
5
use Quantum dots as emitter for the system, it is possible to achieve a single-
photon coupled plasmonic system.
1.1.1 SNOM principles
y
x
screen
Fig.1. 1 Schematic of plane wave diffraction on an arbitrary object
When we consider a general problem: scattering of light by an arbitrary object,

we can have a solution , is the electric field at
any space point . In homogeneous media, electromagnetic fields
can be represented by the angular spectrum representation. By angular
spectrum representation, far-field plane waves as well as evanescent waves
can be described with variable amplitudes and propagation directions (k-vector).
Assume an arbitrary detection screen at the space, the field detected at the
screen is propagating direction z (Fig.1.1). In this screen plane we can have the
two-dimensional Fourier transform of the field:
(Eq.1.1)
, is the wave vector components of corresponding coordinates. Because

we assume the field propagates along z-direction in homogeneous media, we
have , the field can be represented with inverse
Fourier transform:
(Eq.1.2)
6
With
(Eq.1.3)
Which is known as angular spectrum representation. means the position

of light source. is also the propagating constant of the field. When is
real, the field is described with an oscillatory function which can propagates to
far-field, while when is purely imaginary, it is an exponentially decaying
function which only available in near-field. These two situations correspond to
different field waves:
Plane waves:
(Eq.1.4)
Evanescent waves:
Therefore, the angular spectrum is a superposition of propagating plane waves

and evanescent waves. From Eq.1.4, we can find that far-field plane waves has
a limitation of special frequency ( ), higher spatial frequencies are
covered by evanescent waves. Therefore, these high special frequencies

information associated with evanescent waves are lost during propagation to
detector. This limitation corresponds to the diffraction limitation at far-field
observation, which imposes the limit of imaging resolution. This is why we are
interested about the near-field that contains the whole information about the
spatial frequencies of the sample. With near-field microscopy, we can collect
near-field high spatial frequency information by scattering fast decaying
evanescent waves to far-field propagation plane waves. For example, for
illumination-mode aperture SNOM, evanescent waves from the small aperture
are locally scattered by an object [8]. For apertureless SNOM, sub-wavelength
dimension probe locally scatters near-fields of illuminated object [26]. The
scattered light is then detected by a detector placed in the far-field.
7
1.1.2 Information transfer from near-field to far-field
Illuminating
light
Aperture
probe
-z0
0 x
sample
z Detection plane
Fig.1. 2 Imaging information from a sample plane (z = 0) to a detector plane (z = z ) using

an aperture source at z = -z0, z0
Consider the configuration of classic SNOM illumination (Fig.1.2), a probe apex

with aperture is illuminating the sample at near-field region (z0 ). The
aperture is at the plane z = -z0, as a local light source of the system. Sample is
at the plane z = 0, and the far-field detection plane is at plane z = z . Using the
framework of angular spectrum representation (Eq.1.1), we can have the
source field as:
(Eq.1.5)
When the field propagates to the sample plane we have:
(Eq.1.6)
The sample can be characterized by a transmission function .To simplify

the problem, we assume the sample is an infinitely thin object and ignore
topography-induced effects. The scattering field of the sample can be
calculated as:
(Eq.1.7)
8
While in Fourier space, the multiplication becomes a convolution of Fourier
spectrum:
(Eq.1.8)
Then the sample field will propagate to far-field detection plane at z = z ,

therefore we have:
(Eq.1.9)
Obviously, the field been detected is a far-field. We define as

the transverse (in-plane) wavenumber. According to Eq. 1.4, it has to fulfill:
(Eq.1.10)
If we take numerical aperture NA of the collection objective lens into accout we

obtain:
(Eq.1.11)
Fig.1.3 illustrates the process of Fourier space convolution. For the sample
function ( ), the shadow area at center means the low spatial
frequency plane wave ( ), while the gray area corresponds to high spatial
frequency ( ), ie near-field evanescent waves. For the convolution, we
demonstrate two specific points: 1. , the largest transverse
wavenumber for propagating plane wave; 2. , large spatial frequency

at near-field. Here, we only consider the situation of changes at axis. When
, some high spatial signal from sample shift to
propagation wave (gray area inside thick black circle); When

, only gray part inside thick black circle, in other words after
9
scattering, the propagating wave only contains high spatial frequency signal
from sample. High spatial frequencies of the sample, that are combined with
large spatial frequencies from probe aperture, transfer to propagating waves
travel towards detector. Therefore, near-field information are transferred to far-
field and detected.
We also notice that, to transfer information from near-field to far-field, higher

spatial frequency from the sample needs larger spatial frequency wave from
aperture source to combine. The highest spatial frequency that can be sampled
by probe field, according to Eq.1.11, is estimated as:
(Eq.1.12)
For the aperture, the confinement of field depends on its lateral dimension
(aperture diameter), the highest spatial frequencies are on the order of
, so we have:
(Eq.1.13)
When last term can be neglected, thus the field confinement of probe
defines the highest detectable spatial frequencies of the sample, or the theory
resolution of system. However, we have to keep in mind that all above
discussion is highly simplified. Because evanescent waves decay very fast, for
rigorous description, topography-induced effects have to be considered [34].
Besides, in actual experiment, high spatial frequencies are always intermixed
with low spatial frequencies, increases the complexity of interpretation of SNOM
image.
10
Ky
2k
-2k -k k 2k Kx
-k
-2k
(convolution)
Ky Ky
-k k -2k 2k Kx
Kx
= =
Ky Ky
-2k -k k 2k Kx -2k -k k 2k Kx
Fig.1. 3 Convolution of the spatial spectra for sample transmission ( ) and source field
( ).
11
1.2 Light-matter interaction between metallic nanostructure and nano-
emitter
1.2.1 Surface plasmons
Since we choose metal nanostructures for our test sample, it is important to

remind some mechanisms of optical luminescence when metal nanostructures
are involved. The optical properties of metals can be explained from a plasma
model: a gas of free electrons moves against a fixed background of positive ion
cores. Surface plasmons are electromagnetic surface waves with collective
coherent oscillations of free electrons at the metallic-dielectric interface.
Localized surface plasmons are supported by metal nanostructures structures
that can confine optical field to nanoscale dimension, so that to achieve very
strong local enhancement in the case of plasmon resonance, which offers
numerous applications in many domains such as biosensoring, photocatalysis
and integrated optics. [40-45].
Drude model
The Drude model is the well-known model for describing the dielectric constant
of metals supporting surface plasmons [46]. For free electrons of the Fermi sea
experiencing an external electric field , we have a simple equation of
oscillation motion:
(Eq.1.14)
is the electron effective mass, is the electron charge. is the

characteristic damping rate of electron collision. is a harmonic time
dependence of the diving field. With harmonic solution,ns of
the s we can get a dispersion solution from Eq.1.14:
(Eq.1.15)
, whereas is the dielectric constant of high frequency limit, is the

bulk plasma frequency. In small frequencies situation ( ), metals are
mainly absorbing. At higher frequencies ( ), the complex refractive
index is predominantly imaginary, thus mainly reflecting light. In the large
frequencies situation ( ), the damping can be neglected, therefore,
Eq.1.14 can be simplified as:
12
(Eq.1.16)
is predominantly real, and when , metals retain their metallic

character. When , the metallic character is missing, and the bulk
become transparent. Hence, can be seen as boundary bertween metallic
and dielectric behaviors.
Localized surface plasmon resonance (LSPR)
The Drude model is based on free electron plasmonic sea in an ideal bulk metal.
Surface plasmon is caused by collective oscillation of electrons driven by
external electromagnetic field and distribute on the metal surface. This
s an electromagnetic surface wave
propagating at metal-dielectric interface, which is known as surface plasmon
polariton (SPP). The SPP is a TM wave, evanescently confined in the direction
perpendicular to the interface.
When incident electromagnetic waves interact with sub-wavelength metallic

nanostructures, the localized surface plasmons get excited. It is a non-
propagative wave, and the field is confined and evanescent in three dimensions
at nanoscale. When the intrinsic frequency of collective oscillation and the
frequency of external excitation are same, resonance occurs, which is the
localized surface plasmon resonance (LSPR). This resonance causes a strong
confinement as well as high local field enhancement (Fig.1.4). A field
enhancement factor on the order of 10 of more can be achieved [52-54].
Fig.1. 4 a) Localized surface plasmon, shows the electron charge relative displacement in
a metal nanoparticle. b) localized field distribution of a metallic nanoparticle.
The localized surface plasmons might be influenced by nanostructure
13
composition, size, shape, and its local dielectric environment as well as
polarization of the incident electromagnetic fields [47-57]. When the LSPR
takes place at visible wavelength region, the absorption and scattering of
illumination light can be selectively enhanced, thus nanoparticles show bright
colors. For noble metal like silver and gold, their LSPR peak of nanostructures
can be easily manipulated in the visible and near-infrared.
1.2.2 Metal enhanced fluorescence
S1
Vibration relaxation
S0
Fig.1. 5 Simplified Jablonski diagram metal enhanced fluorescence process
When a molecule relaxes from high energy excited state to low energy ground
state, spontaneous emission occurs. Jablonski diagram (Fig.1.5) is used to
explain the physical process of fluorescent emission [54]. After absorption of a
photon, the electron of fluorescent emitter is pumped to excited high energy
state S1, then quickly returns to the lowest energy states of S1 by vibration
relaxation. The excited emitter can go back to ground state S 0 directly by
radiating fluorescence spontaneously with a decay rate or by other non-
radiative transition processes with decay a rate , such as internal conversion
or quenching. The total decay including both radiative decay and non-radiative
decay for all the relaxing channels from S1 to S0 can be presented as:
(Eq.1,17)
The quantum yield reflects a competition between radiative decay and non-
radiative processes:
(Eq.1.18)
And the fluorescence lifetime is the average time of fluorescent emitters remain
at S1 state:
14
(Eq.1.19)
The quantum yield represents the probability of light emission when the
emitter gets excited. The number of emitted photons is proportional to the
number of incident photons, when excitation energy is under saturation. The
fluorescence is strongly influenced by environment. With the presence of
metallic nanostructures at environment of emitters, there is a modification of
radiative decay through the Purcell effect [56,57], thus we can obtain new
express of quantum yield and lifetime:
(Eq.1.20)
(Eq.1.21)
When emitter is placed at suitable distance from metallic nanostructures, an

increase in results in an increase in fluorescence emission intensity,
quantum fields , and reduction of lifetime [58]. Besides, the metallic
nanostructures also have a contribution of enhancement of local incident field.
Especially, when the LSPR of nanostructures is resonantly excited, the field
gets highly confined (corresponding to a strong local density of state),
subsequently increasing the rate of excitation [59,60]. However, considering the
competing of non-radiative decay, if the increase of non-radiative decay is much
bigger than radiative decay, quantum yield may decrease. One non-radiative
process is the energy transfer quenching, with a d -3 dependence to the metal
[59,61]. In actual experiment, quenching usually happens when emitters locate
very close to metal surface (<5nm). Another possibility of non-radiative decay
may be caused by photo-bleaching: if the the excitation energy is very strong,
fluorescence can be stopped [61].
1.3 Summary
Work of this thesis is based on fabrication of active SNOM probe with polymer
tip on fiber end. In this chapter, we briefly introduced the history and
development of SNOM and associated probes, as well as fundamental SNOM
principles of diffraction limit breaking by transforming optical information from
near field to far field. In our experiment, we choose plasmonic nanostructures
as test sample. Thus, basic information of surface plasmon and LSPR have
been reminded. Finally, considering light matter interaction between active
probe and metallic sample, process of metal enhanced fluorescence and
modification of the rate of deexcitation of have been introduced. Chapter 2
15
describes the way we developed SNOM probes based on polymer-tipped
optical fibers.
16
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21
Chapter 2 Photopolymerization for polymer probe
In this chapter, we will introduce how to fabricate a micro polymer probe on

optical fiber end, which could be used as a SNOM probe. This probe will be
further treated to become an active probe. The method of fabrication we use is
based on photopolymerization. We photopolymerize a polymer probe on the
fiber end surface. This probe acts as a scanning mechanical probe providing
topography information of the sample surface. Meanwhile, it can collect the
near field optical signal during scanning. Then we will analyze the actual
working mode of the polymer probe in our experiment. For SNOM, we use the
shear-force mode to control the probe-sample distance during scanning. We
will see how the mechanical properties of the polymer probe have been
improved to meet the requirements of scanning probe microscopy based on
shear-force regulation
2.1 Photopolymerization reaction
Photopolymerization is a well-known and well-developed method for fabrication

of 3D micro and nanostructures [1, 2]. During a photopolymerization process,
liquid formulation is exposed by light, and after absorbing energy from photons,
polymerization happens, so that the monomers in the formulation combine
together, resulting the material curing. Technically, we use a laser source to
trigger the polymerization reaction. The light wave propagates through the
polymer formulation that absorbs the light. Once the absorbed photonic energy
exceeds the threshold of polymerization, the curing process starts. As a result,
photopolymerized structure can be a reproduction of propagating light field.
There are two major components for a photopolymerization formulation: photon

initiator and polymer monomer. Sometimes the photo initiator can be combined
by photosensitive dye and anime co-synergist, while several other different
compounds are added to the formulation to control and improve the
polymerization process. In our experiment, the basic principle is free-radical
photopolymerization [3, 4]. Once light exposes the formulation, the photon
initiator (PI) absorbs the photonic energy, and transform to a transient state(PI*),
which is a mediated steady high energy state. Then it continuously react to a
formation with free radicals R.. The free radicals will react with the monomer
one by one, results in a propagation of free radicals chain reaction. Finally, the
photopolymerization process creates a cross-linked three-dimension structure
with different polymerization degrees depending on the conditions of exposure
The different steps are summarized below
Initiation step:
22
Chain propagation: + .
Final step: .+
+
is the monomer and n, m indicate the number of the monomer in the

chain reaction.
2.1.1 Formulation composition
The monomer used for our formulation is PETA (pentaerythritol triacrylate,

Fig.2.1.a), which is a multifunctional arylate. The photoinitiator is IRGACURE
819 (Fig. 2.1.b). IRG819 is a versatile photoinitiator for radical polymerization
of unsaturated resins upon UV light exposure. It also presents a good 2-photon
absorption [30]. 1% IRG819 is used for our formulation. This formulation is
transparent in the visible, and saturated resins have very weak fluorescence,
which is very important for the active polymer probe, especially with few
fluorescence particles, otherwise it will become background noise during
measurement.
Fig.2. 1 Chemical species contained in the photopolymerizable formulation a) PETA

(pentaerythritol triacrylate); b) IRG819
23
Fig. 2.2 Absorption spectrum of the formulation
The absorption spectrum of the formulation is shown in Fig.2.2, it shows a good

absorption in UV and blue. We will use 405nm laser for 1-photon
photopolymerization.
2.1.2 Polymer stiffness
For the use of polymer tip as a scanning probe, the stiffness of polymer is
important. Thanks to a colleague (Borui Li) of our group and colleagues from
Mulhouse, by adding other initiators into the polymerization formulation, a
different interpenetrating polymer network (IPN) can appear during
polymerization [5][6]. IPN is the polymer comprising two or more networks
interlacing but not covalently bonded. Increasing of special complexity confers
higher cross-link density.
By using a commercial Atomic Force Microscope from Bruker, we could

measure the difference of stiffness of polymers presenting different cross-link
densities. With the peakforce tapping mode technology, the AFM is capable of
a quantitative nanoscale mechanical characteri
modulus [7]. We prepared two samples for these polymers: one is with IPN and
formulation (only use IRG819 as initiator). One drop
of polymer formulation was deposited on a glass substrate, then exposed by
24
UV light spot covering the drop for 10 min, in order to achieve a complete
polymerization.
b
Line1.profile
Line2 profile
Fig.2. 3 AFM stiffness measurement for two different polymers: a) IPN polymer; b) normal
polymer.
Fig. 2.3 are the result of AFM stiffness measurement of these two polymers.
polymer. For the IPN
GPa,
a quite good stiffness among polymers. However, for normal formulation, there
0.25 GPa, slightly smaller than the IPN

formulation, because of the different internal structure. For a x m2 surface,
this polymer presents a lot of areas whose stiffness is much lower than it is at
other parts. As result, the IPN formulation is a better choice for fabricating the
scanning polymer tip, and it is been used in following experiment for our SNOM
probe.
25
2.2 Approach of Fabrication of polymer tip on the surface of cleaved fiber
end
Exposure: laser beam

coupled into an optical fiber
fiber
Position stage
Camera Zoom tube lens
Formulation drop
Fig. 2. 4 Scheme of polymer probe fabrication setup
The setup used for polymerization at the fiber extremity is schematically shown
in Fig.2.4. It consists of a system for coupling a laser beam through the fiber
(not shown), a camera with lens for monitoring the experiment, and a stage for
controlling the position of the optical fiber. For The fiber, we chose s-405xp from
Thorlabs, which supports single mode light propagation from 400nm to 680nm,
thus, almost covers the whole range of visible light wavelength in the single
mode regime. The core diameter of this fiber is 3 µm, and the mode field of
diameter (MFD, see Fig. 2.5) at 405 nm of the fiber is 3.3 µm [5]. MFD is one
measure of the beam width of light propagating in a single mode fiber, and it is
the diameter at which the optical power is reduced to 1/e 2 from its peak level.
Light emerging from the fiber induces photopolymerization. Because
polymerization is directly triggered by the energy of laser power, MFD actually
defines the area where the polymerization process will happen, and could be
approximately considered as diameter of the base of polymer tip.
Fig. 2. 5 Mode field diameter of optical fiber [5]
2.2.1 FDTD simulation for photopolymerization on fiber end
Before doing actual exposure procedure on fiber end surface, we calculate the
26
polymerization process. For this process, we use the model and FDTD (Finite
Difference Time Domain) code from Lumerical [6]. At the fiber end, while light
propagates through the polymer, some energy is absorbed. Once the energy is
over the triggering threshold, polymerization happens, and the refractive index
changes at the polymerized area, then this change affects the light propagation,
which is to say changes the absorption profile.
Therefore, it is a continuously changing process. For calculation, a recursive

algorithm can thus be considered. We assume separating the process with time
iteration. For each time iteration we can calculate the absorption profile
according to the refractive index simultaneously, then we define a threshold for
the absorption intensity which triggers the polymerization. The refractive index
will change because of polymerization, and this new refractive index distribution
will update for the next time iteration, and so on.
To simulate the experiment, we set the parameters as defined by the actual

experimental conditions. The fiber is a single mode fiber, with 125 µm diameter
cladding and 3 µm diameter core. Before polymerization, the refractive index of
polymer formulation is 1.48, and after polymerization, it will turn to 1.52. Here
the calculation is for 1 s, and with a time interval of 0.1 s, it will run over 10 time
iteration for the calculation.
27
|E|^2, t=0.1s |E|^2, t=0.2s |E|^2, t=0.3s |E|^2, t=0.4s |E|^2, t=0.5s
Re(index), t=0.1s Re(index), t=0.2s Re(index), t=0.3s Re(index), t=0.4s Re(index), t=0.5s
|E|^2, t=0.6s |E|^2, t=0.7s |E|^2, t=0.8s |E|^2, t=0.9s |E|^2, t=1s
Re(index), t=0.6s Re(index), t=0.7s Re(index), t=0.8s Re(index), t=0.9s Re(index), t=1s
Fig. 2.6 Simulation for a 1 s photopolymerization on fiber end. Each image represents one
0.1 s time iteration. Upper row shows the field intensity when light propagates through the
polymer prob. The bottom row shows the index distribution above the fiber end.
Fig.2.6 shows the simulation of 10 time-iterations for 1 s total exposure time.

The bottom row shows the changing of refractive index (red area indicated
polymerized material), and the upper row shows the intensity when light
28
propagates through this polymer tip. From the calculation of the refractive index
map, we can notice that this polymer tip is not a perfect cone. When the length
of the tip is about 10 µm, the tip is made of two parts: a big base cone at the
bottom and a pointed tip at the top, and this shape meets quite well with the
experiment result (shown at Fig.2.7).
Fig.2. 7 Polymer tip fabricated from actual experiment, we can see pointed tip at the top,
corresponding to simulation result.
Besides, we notice that when light propagates through the tip, the energy
intensity distribution is not homogeneous. While propagating, the light energy
mostly focuses onto the fiber end surface and the tapered tip at the top. For a
long polymer tip, a part of the light energy gets concentrated at the middle part.
This energy distribution within the polymer tip may influence its mechanical
property as a scanning force probe. Indeed, if we look at the images of the index
distribution, we notice that some part at the middle of the tip do not present a
maximum refraction index, which means this part is not fully polymerized. And
due to energy distribution, this part could not absorb enough energy even with
a post exposure for reinforcement. The resulting mechanical properties will be
further discussed in section 2.3, about the control of the sample probe distance
during scanning.
may more meet the requirement for a scanning probe. We will try to fabricate
such a short polymer tip.
2.2.2 Procedure of Fabrication polymer probe on fiber end
First, a laser (405 nm wavelength) is coupled into the single mode fiber. The
laser intensity is detected at the end of the fiber, to access how much energy
will propagate through the cleaved extremity. This could be regarded as the
29
incident energy used for photopolymerization of the polymer probe at the
surface of fiber end. After setting the triggering energy for photopolymerization,
a shutter allows for controlling the exposure time for photopolymerization. The
fiber end is dipped in a droplet of photopolymerizable formulation deposited on
a glass substrate (see Fig. 2.4). As a result, we get a hemisphere covering the
cleaved fiber end surface after the fiber extremity is extracted from the droplet.
The size of this hemisphere is influenced by the surface tension between the
formulation and fiber end surface, which defines the volume of the formulation
on the fiber end surface. The height of this hemisphere is the limit for the length
of polymer tip in this configuration (Fig. 2.8, left). After setting the shutter time
for exposure, we can open the shutter to trigger the photopolymerization on the
fiber end surface. As discussed in the calculation, during the polymerization,
the polymer will grow from the fiber end to a conic tip. After exposure, the fiber
end is immersed into acetone to remove the unpolymerized formulation. To
make sure the whole polymer tip been completely polymerized, a UV post
exposure is made after polymer tip has been developed by organic solvents.
Polymer tip get reinforced by the post exposure step.
100
Fig. 2. 8 Left: Hemisphere polymer formulation on fiber end surface, long pass filter (>
650nm) used for the camera to avoid polymerization by illuminating light. Right: typical
resulting tipped-fiber after rincing
Fig. 2.8, right, shows a typical resulting tipped fiber. The shape of the polymer
tip highly depends on the parameters used during exposure. In the calculation,
we have shown that the shape of the polymer tip changes with different
exposure times. In experiment, we also adjust the exposure laser power.
Because polymerization is influenced by the whole energy absorbed by the
formulation, changing exposure power and the exposure time influences the
whole exposure energy dose. The relationship between the polymer tip and
these parameters has been studied by researchers of the L2n Laboratory [4, 7,
8]. In order to meet that mechanical requirements for scanning, we have to
fabricate a tip that is as short as possible.
We also manage to fabricate polymer tips with small radius extremity, which
30
may influence the lateral spatial resolution. First, the exposure energy is fixed
through exposure time. In particular, we set the exposure laser energy at 1µW,
and the exposure time varies from 1/8 s to 1/60 s, as shown at Fig. 2.9. From
this example, we find that with different exposure times, the radius of tip
extremity are similar (240 nm, 260 nm, 250 nm, 250 nm), while the tip length
grows with exposure time (Fig. 2.10).
1uw 1/8s 1uw

1/15s
1uw 1uw
1/30s 1/60s
Fig.2. 9 Polymer probe extremity when exposure laser power is 1uw with different exposure
times
Fig.2. 10 Length of polymer tip as the function of the exposure time (exposure intensity =
31
1µw)
Then we fix the exposure time at 1/15 s, and we change the laser power from
1 µW to 500 nW. From Fig 2.11, we can find a clear linear tendency between
exposure power and tip radius. Besides, we notice that with 500 nW, the
polymer tip does not appear after development: with this power, there is no
complete polymerized polymer tip on the fiber end surface after exposure.
Hence, we can consider 500 nW as a threshold with this 1/15 s exposure time
for effective polymer tip polymerization.
32
1uw 900nw
1/15s 1/15s
800nw 700nw
1/15s 1/15s
600nw 500nw
1/15s 1/15s
Fig.2. 11 Polymer probe extremity when exposure laser time is 1/15s with different
33
exposure powers. When the exposure is 500nW, there is no polymer probe but a thin
polymer layer at fiber end surface, as a printing of the base of a former tip. Bottom:
measured radius of curvature of the extremity of the polymer tip as a function of incident
power. A linear tendency is shown from this result.
E1
E2
d1 d2
Fig. 2. 12 Exposure energy over the threshold of polymerization triggering
At the fiber end, the photonic mode has a Gaussian spatial distribution. For a
Gaussian beam, energy is highly confined at its center. During polymerization,
when exposure laser energy decreases, the beam cross section permitting
effective polymerization will also decrease.
Shown at Fig. 2.12, E0 is the threshold energy of polymerization triggering,

when the laser energy decreases from E 1 to E2, the cross section at the
threshold decreases from d1 to d2. As a result, we will get a smaller tip radius
with smaller exposure energy. From this principle, the smallest tip radius we
can fabricate is 100 nm, when exposure energy is 600 nW and exposure time
is 1/15s (see Fig. 2.11). In the other hand, when the exposure intensity is fixed
and the exposure time changes, since the polymerization threshold cross
section is also fixed by exposure intensity, the radius of the polymer tip is then
maintained; while the length of polymer tip grows with exposure time (see Fig.
2.9, Fig. 2.10).
34
To conclude, in this experiment, exposure time defines the length of the probe
tip, while exposure power defines the radius of the tip. Now let us further deal
with the probe length issue. When the exposure time is 1/15 s, the length of the
probe is 5.6 µm (see Fig. 2.10), which is still too long for scanning. However,
when we use 600 nW exposure intensity for getting a small tip radius, if we want
to decrease the probe length by decreasing the exposure time, for example
using shorter exposure time as 1/30 s or 1/60 s, the exposure dose may
become lower than the polymerization threshold, and there is no polymer tip
polymerized. This means that decreasing the length of polymer probe through
the decrease of exposure time is limited by polymerization threshold. As a result,
we cannot fabricate a shorter polymer tip with a very small tip radius.
A method to limit the tip length with certain exposure time is to decrease the
volume of the formulation deposited on the fiber end. This possibility is
illustrated in Fig. 2.13. By controlling the position of the fiber, we can let the
formulation droplet touch a glass substrate. By removing the fiber, the droplet
gets separated and the size of the droplet on the fiber end decreases. We can
repeat this procedure until we get a suitable droplet volume. In general, after
repeating this procedure 4 times, we get a formulation droplet of about 2 µm
height on the fiber end.
Fiber
Fomulation
droplet
Glass substrate
Fig. 2.13 Method for decreasing formulation volume on the fiber end. Top: Schematic
representation. Bottom: typical resulting polymer tip fabricated with 600 nW exposure
35
energy and 1/15 s exposure time.
Fig. 2.13, bottom, shows a polymer tip fabricated by this method. It presents a
we can obtain
a short tip with a relatively small radius. We will preferentially use such polymer
tips as a scanning probe.
2.3 Polymer tip used as a scanning probe
For SNOM implementation, it is necessary to position a probe in very close

vicinity of the sample surface. The scattered light resulting from the near field
light-matter interaction is collected by the detector via the probe. To access the
light-matter near-field interaction, the probe-sample distance should be much
smaller than the wavelength of the light [12][13].
Therefore, we need an active feedback loop to control a stable probe-sample

distance while nanostructure is being scanned (Fig. 2.14). We use a
commercial system from NT-MDT as scanning probe microscopy stage [14].
Setpoint + Controller Amplification

Tuning fork
-
Fig.2. 14 Feedback loop for scanning probe microscopy. The Setpoint is externally defined
corresponding to the measured interaction signal. The controller can adjust the speed and
stability of the feedback loop.
There are several different strategies of distance-dependent feedback signal

for SNOM probes [23-27]. In our experiment, we use the well-known shear-
force method based on the use of a tuning fork [21]. The sample-probe distance
influences the vibration of a probe parallel to the sample surface. The fiber with
polymer probe is glued to one arm of the tuning fork (Fig. 2.15). When the probe
oscillates at the resonance frequency of the tuning fork, the amplitude, phase
and frequency of the oscillation are measured (Fig. 2.16), and all these
parameters can be used for feedback loop in order to control probe-sample
36
distance [15]. The interaction distance range of shear force is about 1-100 nm
depending on the type of probe and sample, as well as the ambient conditions
including humidity, temperature and vacuum level [28,29]. This interaction
range indicates the probe-sample distance during scanning [16][17].
Fig. 2. 15 Fiber with polymer probe glued on tuning fork, right image is the side view zoom
of the tuning fork.
Fig. 2. 16 Oscillation magnitude and phase of the tuning fork detected on our stage as
function of frequency at resonance frequency.
2.3.1 Principles of the shear force regulation
In this shear force methods, the micro quartz tuning forks are originally utilized
as standards in quartz watches. Fig. 2.15 shows a typical quartz tuning fork. A
tuning fork has two prongs with electrodes on the surface. Two electric
connections contacting the electrodes of the prongs are connected to a simple
circuit board, so that this tiny device can be mounted on the SNOM scanning
head, and provide signals to SNOM system. For industrial use, the tuning fork
is encapsulated by a metal cap to avoid the influence of ambient situation.
37
However, we have to remove the protector for gluing the fiber to one prong of
the tuning fork. The common frequencies of this tuning fork are 32 768 Hz or
190 kHz [18].
The mechanical oscillation of the tuning fork prongs leads to surface charges
for its electrodes and can be measured by an external system. Thus, the tuning
fork works as a stress-electricity converter, like piezoelectricity components. In
contrary, when a voltage is applied to the electrodes of tuning fork, it triggers
oscillation of prongs. The designed electrode layout on tuning fork allows us to
detect and excite only movements of the prongs against each other [19].
Fig. 2. 17 Fiber probe with tuning fork installed on scanning stage: a) probe on scanning
head with scanning stage; b) probe landing on glass substrate, bottom half is the reflection
image.
When we use a tuning fork to control the sample probe distance for scanning,
the fiber tip is glued on one prong of the tuning fork. Fig. 2.17 shows the fiber
probe with tuning fork landing on a glass substrate. To make sure that it is the
tuning fork prongs act as oscillating beams and not the fiber itself, the length of
the fiber protruding from the prong should be as short as possible (less than 2
mm). When the tuning fork is landing on the sample surface, it drives a small
oscillation , which can be described by the following equation of motion
[20]:
(Eq.2.1)
(Eq.2.2)
is the amplitude of the oscillation, stands for the time, is the damping
of the system, is the spring constant of the tuning fork, is the driving
frequency, is a constant driving force from the oscillating tuning fork. This
equation is from the model of forced vibration with damping, and is a
viscous dissipative friction force proportional to the velocity. Therefore, we have:
38
(Eq.2.3)
Therefore, from Eq. 2.1 and Eq. 2.2, we can have the expression of steady-
state solution:
(Eq.2.4)
With the classic harmonic oscillator model:
(Eq.2.5)
, is the resonance frequency. And we also have the quality factor (Q-
factor) for damping system as a Lorentzian function:
(Eq.2.6)
39
d
Fig. 2.18. Resonance curve of the tuning fork for different probe-sample distance . The
probe is a 25 µm diameter sharpened gold wire, which protrudes only 75 µm outside the
hows noise spectrum
of the tuning fork with the tip disengaged ( ). The measurements were performed in
vacuum (8×10-7 mbar) at 300 K. [21]
The probe-sample interaction introduces both a viscous friction force

( ) as well as an excess restoring ( ) through the
terms and , respectively [21]. When the probe-sample distance decreases,
the extremity of fiber-polymer tip approaches and interacts with the sample
surface, resulting in the resonance frequency shift and the Q-factor drop, as
well as the decrease of the oscillation amplitude (Fig. 2.18). Both the damping
rate and the spring constant have two different contributions: i) a static or
intrinsic part from the tuning fork based probe itself; ii) an interaction-induced
part from probe-sample interaction. We first discuss the situation of friction force.
In the experiment, we will drive the tuning fork oscillation by a resonance
frequency, which is to say, . At this case, with Eq. 2.4, we can have the
expression of :
40
(Eq.2.7)
stands for the probe-sample distance, is the interaction-induced

damping rate when the probe-sample distance at , while , are
the resonance frequency and oscillation amplitude at this situation. is
static damping rate of the system, when the probe is disengaged from sample
surface, therefore, . Then we can probe-sample interaction-

induced damping rate in relation of :
(Eq.2.8)
Because the resonance frequency of tuning is = 32768 Hz, and the frequency
shift is much smaller than this resonance frequency, we can make the
approximation at Eq. 2.8. According to Eq. 2.3, we can calculate the interaction-
induced friction force:
(Eq.2.9)
Where we use Eq. 2.5 and Eq. 2.6, and the imaginary term indicates the
friction is out of phase with the probe oscillation motion. is the static
spring constant of the tuning fork probe ( ). The oscillation

amplitude is proportional to the voltage signal from tuning fork electrode
(used as the intensity of oscillation amplitude for the scanning system), so we
can have:
(Eq.2.10)
41
From this expression, we can figure out how the probe-sample distance is
controlled with friction force. When the probe gets close to the sample surface,
interaction happens between probe and sample, thus an in- plane friction force
works on the probe, and the oscillation amplitude decreases from the free
space situation. This decrease is detected by the scanning system through a
drop of voltage. With a feedback loop, the system adjusts the distance between
therefore, the probe scans with a constant interaction force, in the other word,
at a constant distance from the sample surface. This is also the strategy that
we use in actual experiment. For example, we will set an oscillation amplitude
voltage at 90% of the original voltage , as the feedback setpoint.
Now let us turn attention to the probe-sample interaction induced elastic force.
Similarly, the probe-sample interaction induced equivalent spring constant
can be obtained with relation to static spring constant . With Eq. 2.5, we
have:
(Eq.2.11)
So that:
(Eq.2.12)
When , is the shift of resonance frequency. Therefore, we can

obtain the expression of probe-sample interaction induced elastic force:
(Eq.2.13)
From Eq. 2.13 we know that it is also possible to control the probe-sample
distance by considering resonance frequency shift, with feedback loop.
Theoretically, frequency associated probe-sample distance controlling system
may even have a faster response speed than the one with amplitude associated.
42
2.3.2 Effect of the probe compliance
To make sure this shear force probe-sample distance control system works well,
it is important that the probe remains stiff in order to ensure maximum damping
of the tuning fork. The condition to fulfill is that the probe-sample induced
deformation amplitude of probe itself should always be smaller than the tine
amplitude of tuning fork. Because the fiber has a
we can focus our attention on the polymer probe. Assuming a cylinder geometry
for our polymer probe, we estimate its spring constant using [22]:
(Eq.2.14)
Where is the radius of the probe cylinder, is the length of probe, and
approximately consider as , , and Youn

polymer has been measured at Chapter 2.1.2, as . Therefore, with Eq.14,
we can calculate .
As we discussed above, in our experiment, we use oscillation amplitude voltage

signal to control probe-simple distance by feedback loop. From Eq.2.10, we
know that we are actually controlling probe-simple interaction induced friction
force, which also leads to deformation of polymer probe itself:
(Eq.2.15)
With the condition that probe deformation should be smaller than tuning fork
oscillation amplitude, , we can have the requirement

for :
(Eq.2.16)
The typical spring constant of tuning fork [20][21], and

for polymer probe in experiment, we can obtain the available
setpoint range for the system:
43
(Eq.2.17)
For example, if we set the original amplitude voltage at 10 mV (for example,

adjusted by the gain of amplifier), we can only use a setpoint voltage bigger
than 9.97 mV. In the experiment, a smaller setpoint means a closer probe-
sample distance, meanwhile, a bigger range of available setpoint may have
less influence by system noise. We can increase this setpoint range by
increasing the probe spring constant, that is to say, a harder probe. According
constant. Therefore, we can try to fabricate shorter and thicker polymer probe
during polymerization, in order to have better mechanical property. For example,
if the length of polymer probe could be shortened by half, which is to say,
become , we can have , therefore , 8
times bigger than the original setpoint range. Similarly, we can have stronger
probe if we increase the cylinder radius of probe.
To conclude, about a polymer probe used for scanning, it is important to have

a stiff probe so that the shear force can be well detected by tuning fork
configuration. For a given material, we have to fabricate a short and thick probe
to promise its stiffness. In actual experiment, we usually use 9.95 mV with
respect to the original amplitude at 10 mV, to scan the nanostructure with a
smallest probe-sample distance. During experiment, the probe has first to be
landed to the sample surface. As probe approaching to sample surface, probe-
sample interaction occurs, oscillation of probe decreases, thus voltage signal
of tuning fork decreases from original amplitude 10 mV to 9.95 mV, and stop
the approaching process. Then scanning will operate at this setpoint by
feedback loop, maintaining this probe-sample distance as constant height
mode. Because the probe is always oscillating, the noise of height signal is
originally caused
closer to the sample surface, the probe has smaller oscillation amplitude,
therefore, the height signal of topography image has a smaller system noise.
However, if probe is over approached, the probe cannot follow the oscillation of
tuning fork, the system noise of height signal is increasing. Shown as Fig. 2.19,
when the setpoint is 9.95 mV (Fig. 2.19.a), the noise is about 5 nm, while the
setpoint is 9.90 mV (Fig. 2.19.b), the noise is about 30 nm. In the other word,
the limit of setpoint is between 9.90 mV to 9.95 mV, which matches well with
the calculation result 9.97 mV.
44
a b
Fig. 2.19 Height signal of topography image when scanning on glass substrate with original
oscillation amplitude signal at 10 mV: a) setpoint at 9.95 mV; b) setpoint at 9.90 mV
2.4 Summary
In this chapter, we described the procedure of photopolymerizing a polymer

probe at the extremity of an optical fiber for scanning probe microscopy. We
first optimized the formulation for polymerization, to improve the stiffness of
polymer, so that the polymer probe can have a good mechanical property for
probe-sample distance controlling. Then we studied the parameters of
photopolymerization influencing the shape of the polymer probe. We finally
found suitable parameters to fabricate a probe which can meet most of the
requirements of our experiment. Furthermore, we also analyzed the method for
probe-sample distance controlling by using shear-force tuning fork strategy, in
order to carry out scanning probe microscopy on nanostructures.
45
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47
48
Chapter 3 Attachment of few fluorescence emitters on
polymer at different scales
In this chapter, we will discuss the method of attaching few fluorescence

emitters on polymer probe, to fabricate an active SNOM probe. First, our home
made optical system will be introduced. This system can be used for monitoring
active probe fabrication process as well as characterizing result of fabrication
of active probe. We will discuss two different strategies of attaching emitters on
the polymer probe. One consists of a surface functionalization of the whole
polymer probe for grasping emitters from a glass substrate, while the other one
aims at functionalizing specific area on the polymer probe for attaching emitters
from colloid emitter solution. Two different emitters will be considered: doped
fluorescent polystyrene nanospheres and semiconducting Quantum Dots.
Furthermore, we have extended these attaching strategies on gold nanocubes
to which polymer nanoparts have been integrated beforehand, to obtain hybrid
plasmon-emitters integrated on a substrate.
3.1 Optical system
Besides of distance control for scanning, a good optical set-up is crucial for
SNOM. For further treatment of nanostructures and emitters, objects have to
be well monitored. In our experiment, the optical system is homemade. It is
shown in Fig. 3.1. Two light paths have been developed: reflection and
transmission. The reflection path corresponds to light that comes from the
objective lens, reflect at the sample surface, and is collected by the same
objective. It can work without probe. In that case, the same objective lens is
used for sample excitation and light collection. As a normal observation method,
thanks to the camera and optical detectors, by using this light path, we can
locate and analyze the interesting part on sample before the probe landing on.
When the probe landing on the sample, it may become a tip enhanced signal
[2]. The transmission light path corresponds to light collected from probe to fiber
then to the detector, while the incident light is focused by the objective lens.
Alternatively, the probe can be used for locally shining the sample and the
transmited field is detected by the objective. The detectors can be spectrometer
or single photon counter (APD: Avalanche Photon Diode), therefore both
spectrum and time resolved photoluminescence is possible on the stage. It may
have a filter before the signal been collected to the detector so that we could
measure the fluorescence signal from the sample. When the polymer probe
scans on the sample, its extremity will also work as a micro lens for either
detection or illumination.
49
Transmission light path
Prism
flection light path
Fig.3.1 Schematic of scanning optical microscopy system. Detector can be either

Avalanche Photo diode or spectrometer.
3.1.1 High resolution confocal observation system
The reflection light path is a confocal system. The incident laser beam
illuminates the sample from bottom, through a 100x oil objective, with 1.4 N.A.
The incident laser beam is deflected to by a semi-transparent mirror, while the
reflected light can propagate through this mirror for observation. Then the
reflected light separates to two light paths by a 50/50 beam splitter, one to
camera, monitoring the sample real time status, and the other to a focus lens
so that the signal could be coupled into a fiber for detection. The fiber core acts
as a pinhole, and the laser beam is focused to irradiate the sample. When the
sample stage is scanned, we can have a point-to-point sample image from
reflection light. Thus, before the SNOM probe lands on the sample surface, the
reflection light path is used for characterizing the nanostructure on the sample,
as a confocal microscopy configuration (shown at Fig. 3.1). Filters can be
inserted into the light paths, to remove the excitation light for fluorescence
signal measurement.
In our experiment, since we use a high NA objective lens to focus laser beam,
the focused laser spot may play a role as probe. The resolution of such an
scanning image depends on the size of the laser spot whose radius x is
50
calculated from the size of Airy pattern through the objective, provided that the
whole entrance pupilla is illuminated [3]
(Eq.3.1)
When the wavelength of laser is 530nm, . Therefore, 230 nm is the

theoretical resolution of this scanning image system. The core of the detection
fiber has been choosen to actually take advantage of this spatial resolution.
Because the signal is coupled into a fiber, in the region of fiber operating
wavelength, we can measure the spectrum of the signal from the sample. With
this imaging system, we can characterize the sample and easily localize the
nanostructures on the glass substrate (Fig. 3.2).
Fig.3.2 Confocal scanning image for two nanostructures, illuminating by 530 nm laser. The
left is a silver nanowire of 115 nm width, the right is a gold nanocube of 130 nm side length.
In the image, the apparent minimum size of particle is more than 200 nm, limited by
diffraction.
3.1.2 Time-resolved Photoluminescence measurement
Apart from imaging and spectrum, we can also do time-resolved

photoluminescence measurement on this set-up. For example, in our
experiment, fluorescence lifetime is an inherent feature of the emitters. On the
other hand, the lifetime is highly sensitive to its environment [4]. Our goal is to
integrate emitters on the extremity of a SNOM probe, thus, the fluorescence
lifetime may change compared to emitters in solution or on glass substrate.
Furthermore, when such a active probe scans on metal nanostructures, the
emitters will have some plasmon-emitter interaction with metal nanostructure
(e.g Purcell effect) which also leads to a significant change of lifetime decay
[15-17].
51
Fig.3.3 TCSPC technique for fluorescence lifetime measurement [5].
Time-Correlated Single Photon Counting (TCSPC) [5] is the technology we

have used for time-correlated photoluminescence measurement. During test,
sample is excited periodically, usually by picosecond or femtosecond laser
pulses, speed enough to meet requirement of sample lifetime at nanosecond
range. The single photon events are collected over many cycles, and
reconstruct the fluorescence decay profile. Fig. 3.3 shows how the fluorescence
decay result forms over multiple cycles. Fluorescence is excited repetitively by
short laser pulses. The time difference between excitation and emission is
measured by time tagging electronics acting like a stopwatch. For each cycle,
the timing starts when the pulse is triggered by the pulse laser synchronization
signal, and stops when a photon is detected by the photon counter. This time
difference of arrival will be recorded, and sorted into a histogram. Considering
virtue of quantum mechanics, the actual count arrival times are random, finally
this histogram shows the photon count distribution with time of arrival. Since
the intensity of light is determined by the number of photons emitted in any
52
period of time, it is directly proportional to the surviving population of excited
molecules. The histogram we get is equivalent to the decay profile of
fluorescence. Lifetime can be calculated by fitting the profile.
The decay curve exhibits a single-exponential or multi-exponential decay, which

depends on the amount of fluorescence lifetime components. Thus, the
fluorescence decay could be defined as follow,
(Eq.3.2)
, where , are, respectively, the amplitude and lifetime for each fluorescence
decay species. In actual experiments, the signal detected is characterized by
the convolution with the system time precision, therefore, we can have the
following expression
(Eq.3.3)
IRF is the Instrument Response Function, which summarizes overall timing

precision from both detectors and electronics of the system. The total IRF is the
convolution of all component IRFs. If the system is ideal, with an infinitely sharp
excitation pulse (delta pulse) and infinitely accurate detectors, we will have an
infinitely narrow IRF, as a delta-function. In this case, the lifetime profile curve
can be well fitted by exponential function. For the actual experiments, we will
measure the IRF, a typical approach is to replace the band pass filter for
fluorescence to Neutral-density filter, so that no fluorescence signal but some
scattered excitation light is reaching the detector. Fig.3.4 shows an example of
lifetime analyze for an emission of QD with two decays. After photo-excitation,
a QD could lose one of the photo-generated charges and ionized, the ionized
QD absorbs another photon, it could result a trion state. The extra charge brings
in an additional radiative recombination pathway for the trion state (a three-
carrier state, presented by ionized QD when the QD losing photo-generated
charge during photo-excitation), therefore, it has a shorter decay lifetime than
the neutral QD [18-20]. The red curve is the IRF, and the blue curve is the
fluorescence intensity profile from the sample. The result is calculated by the
iterative reconvolution method according to Eq.3.3, and it shows two decay
times: 4 ns and 1.3 ns -AQRH
Single-Photon Counting Module [7] as a photon detector (time precision at
ns, which represents the time

precision for the whole system.
53
Fig.3.4 Example of lifetime analyze for an emission of QD with two decay system.
Calculated by Fluofit from PicaoQuant [9].
3.2 Attachment of single emitter from glass substrate
To achieve an active SNOM probe, it is important to make sure that only a few
emitters get integrated on the extremity of the micro polymer probe, so that by
scanning, we have a very small local light source interacting with the sample
nanostructures. One method is to chemically functionalize the whole surface of
the polymer probe, covering adhesion group the probe surface (See Fig.3.5).
The considered functionalization is based on the chemical grafting of amine
molecules on acrylic monomers by Aza-Michael addition reaction [21,22]. It is
a conjugate addition reaction of nitrogen donor nucleophiles to electron
deficient olefins. After functionalization, polymer surface is positively charged
due to the presence of amine group, therefore, the negatively charged
nanoparticles can be assembled by electrostatic interaction [23].
54
a
Functionalized PETA
Fig.3.5 a) PETA monomer is functionalized by DEA (Diethylaine) according to Aza-Michael

addition reaction; b) Functional groups on the polymer surface and on the nanoparticles
that leads to their assembly on the polymer surface.
Our experimental approach consists in approaching the polymer probe to the

single emitter that has been deposited on glass substrate. When the polymer
probe touches the emitter, it will be attached to the probe extremity. The
advantage of this method is that we can characterize and select the emitter in
advance, and attaching the exact emitter to the polymer probe.
Fig. 3.6 Absorption (dashed line) and emission spectrum of fluorescence nanospheres.
The green line indicates the wavelength of laser excitation, and the orange rectangular
shadow is the range of the filter used for detection.
First, we have to prepare a sample with separated emitters on the glass

substrate. We have choosen commercial fluorescence polystyrene
nanospheres (FluoSpheres F8801; Invitrogen, surface modification with
carboxylate) as emitters. They are polystyrene spheres enveloping dye
molecules which have an absorption peak at 580 nm, and an emission peak at
605 nm (see Fig. 3.6). The diameter of the nanospheres is 50 nm. Nanospheres
55
have to be well separated, so that it is possible to attach single (or few)
nanosphere from glass substrate.
a b
Fig. 3.7 Characterization of 50 nm fluorescence nanospheres on glass substrate: a) Image

obtained by Scanning Electron Microscopy (SEM); b) Image obtained by Atomic Force
Microscopy (AFM).
By using SEM and AFM imaging (Fig. 3.7), we can adjust the concentration of
nanospheres within the colloidal solution, and finally get an ideal sample for the
attaching procedure. Then, on the developed optical set-up decribed in section
3.1, we can get the fluorescence image of the sample (Fig. 3.8.a). This
fluorescence image was obtained with the confocal configuration using the
reflection light path in Fig. 3.1 (without SNOM probe involved). The sample is
excited by 530 nm laser, and filtered by 570 nm high-pass filter. This
fluorescence image confirms the presence of fluorescent nanospheres on the
glass substrate.
56
a b
c d
Fig. 3.8 Scanning fluorescence and topography image of nanosphere on glass substrate:
a) confocal fluorescence image of 5x5 m2 area on glass substrate of separated
nanospheres; b) topography image of chosen single nanosphere (nanosphere in red
square at former image) obtained by shear force microscopy using a fibered polymer probe;
c) fluorescence image of a single nanosphere from transmission light path, using the
polymer probe as a local optical probe; d) fluorescence image of a single nanosphere from
reflection light path (same mode as for figure a)
We choose an isolate nanosphere for attaching it on the extremity of the fibered

polymer probe. This nanosphere is highlighted by the red square in Fig. 3.8.a.
For the attachment, we have to align polymer probe to the position of
nanosphere. Therefore, before probe chemical functionalization, the polymer
probe is landed on the sample surface, so that the single nanosphere can be
characterized with the probe itself and aligned with the position of probe.
Another Laser beam is also coupled into the fiber of probe: light propagates
through fiber and is focused at the probe extremity. We can observe the focused
spot of probe extremity. Because the bottom laser beam is fixed, we can move
the probe, and let the spot from probe spatially overlap the bottom illuminating
laser spot. Due to reciprocity, now the bottom illuminating light can be coupled
through probe to fiber, signal can be detected from the other end of fiber as
transmission light path, and in this situation, the reflection light path and the
transmission light path permit the observation of the same area. Now if we scan
the sample, we obtain the topography image (Fig. 3.8.b), transmission
57
fluorescence image (Fig. 3.8.c) and reflection fluorescence image (Fig. 3.8.d)
of the single nanosphere simultaneously, these images carry the information
from nanosphere, meantime indicate probe-nanosphere relative position.
Then the polymer probe would be functionalized, so that it may have the ability
to assemble with nanosphere. The probe is removed from the scanning stage
and immersed into formulation for functionalization for about 30 minutes. After
functionalization, we reinstall the probe back to scanning stage and approach
the functionalized polymer probe to the sample surface. Because the sample is
not moved, we can retrieve the same sample area and attach the pre-identified
nanosphere. We use the transmission light path to align the probe position.
When the probe approaches the sample surface, the illuminating laser through
the stage can be collected by the probe. Before the probe touches the sample
surface, because the laser position is fixed, we can scan the probe to know the
relative position between probe and laser spot, then align the probe to the
position of laser spot. However, when we remove the probe, to protect the probe,
we retract the probe about 1000 m away from sample surface, it is difficult to
maintain this alignment during approaching. To solve this problem, we align the
probe for each 100 m approach step. Furthermore, before landing, the
sample is slightly moved with the piezo stage, so that we can land the probe on
an empty and clear area at the glass substrate, in the vicinity to the nanosphere
to be picked up. After the probe landing on the sample surface, again, we move
the probe, adjust the focused light spot from probe overlap the bottom
illuminating light spot. After the probe has been well aligned, we switch from
probe scanning mode (for probe moving) to stage scanning mode, in order to
move the nanosphere back to the position of the probe and illuminating light
spot area. Then, the probe is kept in contact with the nanosphere for 30 min, to
make sure the adhesion between probe and nanosphere is completed.
58
Fig. 3. 9 Fluorescence spectrum of nanosphere attached on polymer probe.
a b
Fig. 3.10 Fluorescence of single nanosphere on the glass substrate (scanning confocal
image), a) before attachment; b) after attachment (same area), scanning is been stopped
when the former fluorescence area is checked.
Afterwards, we check the attaching result on the probe. The probe after
attachment is landing to the sample surface and positioned at the spot of bottom
illumination laser, and fluorescence spectrum is measured from bottom
reflection light path. Fig. 3.9 shows the fluorescence spectrum from nanosphere
attached on polymer probe, which has a peak at 603 nm, in keeping with the
59
spectrum of nanospheres in free space. To avoid the nanosphere photo-
bleaching due to strong excitation energy, we only use quite low energy to
excite the emitters. As a result, the fluorescence signal is very weak.
When the attaching procedure is completed, we retract the probe from the
sample surface, if the nanosphere successfully attached to the probe, the
nanosphere will leave the glass substrate with the probe. Therefore, if scanning
the stage, the fluorescence signal can no longer be observed by the reflection
light path, through scanning confocal image (Fig. 3.10).
1 2
Fig. 3.11 Fluorescence intensity from reflection light path when probe with nanosphere is
placed at different distance from the sample surface where the incident exciting beam is
focused. Part 1: 1 m from sample surface (feedback loop open); part 2: landing on the
sample surface.
Additionally, we retract the probe at a small distance to a focus-off plane (for

example, if we open the feedback loop, the probe will retract about 1 m), we
observe intensity change of the fluorescence, as shown in Fig. 3.11. In this
figure, from 0 s to 20 s, no excitation light illuminates the sample; from 20 s to
40 s, the active probe is 1 µm away from sample surface, there is a weak
fluorescence signal; from 40 s to 70 s, the active probe is landing sample
surface, the fluorescence signal is 2 times bigger than the former away case;
after 70 s, the active probe is removed from the illumination spot, so there is no
fluorescence signal anymore, the noise of signal is from environment.
60
We also characterized this active probe (with attached nanosphere) by SEM.
However, this characterization is sensitive. Indeed, we noticed that SEM
imaging may kill the fluorescence. On the other hand, the typical fiber length for
a SNOM probe is 1 m. For a SEM measurement, we usually have to cut the
probe extremity from the fiber shaft. Fig. 3. 12 is typical SEM image of a
. From this image, we notice that the
nanosphere is not attached at the center of probe, because of the difficulty of
alignment. As mentioned in section 3.1.1, the optical resolution for the far-field
system is limited by the diffraction limit, and when we use 530 nm laser as
illumination light, the resolution of system is about 230 nm. Consequently,
during attachment, when we align probe to the illumination light spot, the error
is also limited by the system resolution. From Fig. 3.12.b, we can find the
nanosphere is located at about 200 nm away from the center of probe extremity,
matches the system resolution 230 nm. Meanwhile, when the probe is landing
on sample surface, the probe may have small tilt angle, not perfectly
perpendicular to the sample surface, so that it is not the center of probe
extremity touching the sample surface, but surrounding area, which also could
lead to center offset of the nanosphere during attachment. Because the
nanosphere only has a soft polymer envelop, it is been squeezed from sphere
to disk after attachment (shown as Fig. 3.12.b). In chapter 4, we will use this
active probe to scan nanostructures, and more information will be provided in
this chapter.
a nanosphere b
nanosphere
Fig. 3. 12 SEM image of polymer probe attaching nanosphere, a) 40k magnification; b)

100k magnification.
3.3 Attachment of emitters on an extra tip obtained by second exposure
on polymer probe
In last section, we introduce a method with the probe is totally surface

functionalized. Then we control the polymer probe touching the fluorescence
nanosphere on glass substrate. To obtain an active probe with few emitters,
61
though the whole probe surface is possible to assemble nanospheres, we
select a single nanosphere on optical observing stage to be attached.
In this section, alernatively, we can first control the functionalized area on probe
and immerse the probe into of solution of nanosphere, so that nanospheres
only attache to the certain area which has been prefunctionalized. Though the
probe is immersed into an environment that contains a lot nanosphere, only a
s. Finally, we also obtain
probe
Our strategy is to do a second exposure on the polymer probe, in order to

fabricate a second nanotip on the polymer probe. The photochemical
formulation used for fabricating this second nanotip is functionalized [23], while
the first tip is made with a usual polymer. As a result, ultimately, we get a
functionalized second nanotip. Because the first base polymer probe has not
been functionalized, only the second nanotip is expected to enable attachment
of nanospheres. Then we immerse the polymer probe into the solution of
nanospheres for one hour, and the solution is made vibrate by ultrasonic for
about 10 min, to help the nanospheres keeping isolate within the solution, so
that we do not attach a big cluster of nanospheres to the probe.
a b
c d
Fig. 3.13 SEM of second tip on polymer probe for attaching nanosphere: a) second tip on
polymer probe; b) zoom for image a); c) nanosphere attached on the top of the second tip;
d) nanosphere attached on bottom of second tip.
62
To fabricate the second tip, we use the same monomer and photo initiator as
for the formulation used for the first tip. However, 5% inhibitor is added into this
second formulation. Inhibitor prevents the generation of free radical during
polymerization [10]. Consequently, the use of inhibitor leads to the increase of
the exposure energy threshold, and a shrink/squeeze of the volume of
polymerization, which help us to fabricate a smaller tip. Fig. 3.13 a,b show an
example of double tip obtained by this double-exposure process. From the our
revious studies [24,25], it is known that the laser exposure dose
influences the length and radius of the tip. Our goal is to integrate fluorescence
nanosphere to a polymer probe for scanning probe microscopy. As we
discussed in chapter 2, long tip may increase the difficulty of scanning. Another
disadvantage of long second tip is that we cannot control the position of
attached fluorescence nanospheres, because the whole second tip is
functionalized, as illustrated in Fig.3.13 c,d, showing that both top and bottom
of the second tip may attach nanospheres. Therefore, we do not want a typical
long tip, while a tiny point at the extremity of the polymer probe is an ideal
solution at this situation. Like the base polymer probe, when the exposure dose
is close to the threshold, a thin layer can be polymerized, rather than a
cylindrical tip. By using exposure dose just over the threshold, we can get a
functionalized polymer point at the extremity of the polymer probe. After
immersion within nanospheres-containing solution, we rinse the probe by a big
amount of water, so that there is no other place except the extremity that can
attach the nanospheres. Figure 3.14 shows an example of result: nanospheres
can attach exclusively at the extremity of the polymer tip.
a b
Fig. 3. 14 Polymer probe with a functionalized thin polymer layer at its extremity, rather
than a long second tip: a) before attachment; b) after attachment.
In Fig. 3.13 and Fig. 3.14, the attachment of 200 nm nanospheres was
demonstrated. We preferred to use smaller (50 nm) nanospheres for
attachment, to obtain a higher optical resolution during scanning. However, we
noticed that the 50 nm nanospheres can easily attach to the polymer probe
surface without functionalization by Van der Walls interaction, due to its higher
surface to volume ratio (see Fig. 3.15 as an illustration). As a result, it has
turned out that we cannot selectively integrate 50 nm nanospheres to the
63
extremity of polymer probe using the approach introduced above. If we want to
control the attachment of 50 nm nanospheres, we have to adjust the
functionalization formulation, as well as other parameters of the nanosphere
solution (for example, ligand on nanosphere surface, concentration of
nanosphere, solvent of solution er, an ideal parameter has not been
found during this thesis.
Fig. 3. 15 50 nm nanospheres attached on polymer probe without functionalization.
Hence, the strategy based on a second functionalized tip is promising but

turned out to work only for the 200 nm nanospheres in this experiment. Another
problem is that the second tip strategy suffers from lack of effective real-time
monitoring method during attachment, compared to the substrate-attaching
strategy described in section 3.2. It is thus much more difficult to control the
parameters during experiment, resulting in a low reproducibility. Therefore, we
will use the strategy described on section 3.2 for further studies.
Another way to integrate nano-emitters on the probe extremity is directly add

nano-emitters into the formulation used for the second exposure (as it was done
in ref. [11]), so that after, exposure, the tiny polymer point polymerized at the
probe extremity contains nano-emitters. For this approach, nanospheres are
too big as nano-emitters, it may influence the polymerization process. Thus, we
use Quantum Dots (QDs) as nano-emitters in the photopolymerizable
formulation. Here we use red CdSe/ZnS QDs (emission at 620 nm). The size
of QD is less than 10 nm, and it could be synthesized by the colloid chemistry
method. According to some result of other experiment from our group, such a
QDs-containing formulation can polymerize like normal formulation. Only the
exposure dose threshold tends to slightly change due to the absorption of QDs
[11]. Then we can try a same exposure process from former experiment of
attaching nano-spheres, to find the exposure dose threshold and polymerize a
64
smallest polymer dot. We could get polymer dot has 100 nm radius at the
extremity of polymer probe, which may contain a lot of QDs comparing the size
of QD (10 nm), however, we could decrease the concentration of QDs been
added into the formulation, to decrease the QDs been integrated to the probe
extremity. In Fig. 3.16, we can find the second tip containing QDs been excited
by the 405nm laser through fiber, excitation light is filtered by high-pass filter.
a b
Fig. 3. 16 Second tip containing QDs excited through fiber by UV light. a) polymer probe
on fiber end with second tip containing QDs; b) zoom-in of the extremity of polymer probe
observed through a 100x objective lens.
3.4 Hybrid nano-emitters based on the local intergration of quantum nano-
emitters to vicinity of plasmonic nano-structures
In the previous section we discussed how to integrate fluorescent emitters at

certain location of submicron polymer structure. In this section, relying on the
experienced acquired in the previous studies, we report on experiments of
nanophotopolymerizaton at gold plasmonic nanostructures. The polarization
sites are controlled by the local plasmonic near- field: only the sites where the
plasmon-enhanced optical field can trigger the photo polymerization process.
We have taken advantage to polymer engineering. By using either
functionalized polymers or QD-containing formulations, we can place the
emitters at polymerized parts, like what we did for the second tip on polymer
probe. With this method, we have integrated nano-emitters in the vicinity of gold
nanocubes, resulting in unique hybrid plasmonic fluorescent nano-structures.
3.4.1 Principle
The gold nanocubes used in the experiment where synthesized by Sylvie
65
Marguet from CEA Saclay [12]. These nanoparticles are in water solution, and
have to be deposited separately on ITO glass substrate for further test. ITO
glass is suitable for SEM observation. The length of the edges of the nanocubes
is 130 nm, as shown by SEM and AFM images (Fig. 3.17). We can also notice
that the naocube has rounded edge with corner radius of curvature of about 3
nm.
a b
Fig. 3.17 Characterization of single gold nanocube: a) SEM image; b) AFM image.
By measuring the dark field scattering spectrum of single nanocube, we know

that it has a main plasmon peak at about 670 nm (Fig. 3.18). This peak
corresponds to the dipolar localized surface plasmonic resonance (LSPR) of
nanocube [26,27]. This LSPR undergoes a 100 nm red shift when the nanocube
is inside the polymerization formulation during photopolymerizaiton, that is to
say, up to 770 nm. LSPR indicates a wavelength with which the light will have
a strongest enhancement at the surface of the nanocube. This strong local
enhancement leads to a significant energy confinement at the vicinity of
nanocube, which has helped us fabricate a very small polymer structure at the
surface of nanocube.
To match this LSPR, we used two photon polymerization (TPP) for the
experiment. Compared to one photon polymerization (OPP) we used for
fabricating the polymer probe (described at Chapter 2), TPP is a nonlinear
process that is excited by two photon absorption of light [13]. During exposure
in the near-infrared, the photon initiator can be activated by absorbing two
photons simultaneously, for a single quantum event the energy corresponds to
the UV region spectrum, which is for the initiator (IRG819) used in this
experiment. The polymerization rate of TPP is proportional to the square of
photon intensity, which leads to a much higher 3D spatial accuracy than for
OPP to place the polymer nanostructure very close to the gold nanocube.
66
Fig. 3.18 typical scattering spectrum of a single gold nanocube in air, on the glass substrate.
For photopolymerization, a 780 nm femtosecond Ti:Sapphire laser was used

for exposure. The incident laser is focused by an objective lens (N.A. = 0.6),
and the single nanocube is observed by dark-field white light illumination, so
that we can easily locate the nanocube at the position of laser spot. Because
of the strong local energy enhancement at the nanocube surface, we use an
exposure dose weaker than the polymerization threshold without nanocube.
The threshold dose (Dth) is measured previously at the empty area of the
sample. The near-field energy decreases very fast away from the nanocube
surface. By using different exposure dose weaker than Dth, we can take
advantage of the plasmon enhancement and integrate different nano-volumes
of polymer polymerized on the surface of nanocube. In general, the obtained
photopolymerized nanoparts reproduce the near-field energy distribution [28].
Fig. 3.19 shows typical resulting hybrid nanostructures with two cube
orientations with respect to the incident X-polarization.
67
Fig. 3.19 SEM images of the hybrid structures on gold nanocube resulting from plasmonic,
with exposure of incident polarization along the x-direction: a) cube side edge parallel to
the incident light polarization; b) FDTD calculation of near-field plasmonic intensity used
for plasmonic TPP resulting in a); c) diagonal parallel to the incident light polarization; d)
FDTD calculation of near-field plasmonic plasmonic intensity used for plasmonic TPP
resulting in c).
In that way, different polymer nanovolumes on nanocube can be obtained,

through the control of the plasmonic near-field energy distribution.
We have taken advantage of this specific approach to locally integrate nano

emitters in the vicinity of the gold nanocubes, through two approaches that are
described below.
3.4.2 Attachment of fluorescence polystyrene nanospheres on gold
nanocube
When the polymer is functionalized with adhesion group, fluorescence
68
polystyrene nanosphere can be attached, like what we did for active probe. By
immersing the hybrid nanostructures shown in Fig.3.19.c into nanosphere
solution, nanospheres can selectively attach to the surface of functionalized
polymer. With different polymer thicknesses, we can control the distance
between the emitters and the nanocube [28]. In Fig. 3.20 we see that with higher
exposure dose used for photopolymerization, the polymer thickness on
nanocube surface is bigger, resulting in many attached nanospheres
(Fig.3.20.a), For weaker thickness, only a few nanospheres attach to the
nanocube (Fig.3.20.b).
(c)
Fig. 3. 20 fluorescence polystyrene nanospheres attached on the surface of nanocube with

different polymer thicknesses corresponding to different photopolymerization exposure
dose: a) 40% Dth; b) 10% Dth. c) SEM image of different size of polymer exposure by
different exposure dose from 80% to 10%.
After the nanospheres attached to the vicinity of nanocube, they could be

selectively excited by the local surface plasmons of nanocube. By changing the
exposure dose during plasmonic TPP, we can get different polymer thicknesses.
69
This thickness acts as spacer between the nanocube and the nanoemitters. We
analyzed the lifetime decay for the emission from these different hybrid systems.
In Fig. 3.20, we can see the lifetime of fluorescent nanospheres decreases
when exposure dose decreases. When exposure dose decreases, due to the
weaker polymer thickness, the attached nanospheres get closer and closer to
nanocube, resulting in a shorter lifetime through the Purcell effect. The free
space lifetime of nanosphere can be fit by exponential function about 6.3ns.
And the fastest decay in Fig. 3.21 is close to the IRF (instrument response
function), which is about 0.6 ns, indicating the resolution of the experiment
system. Thus, lifetime of nanospheres decreases from 6.3 ns (at free space) to
less than 1 ns. One the other hand, From Fig. 3.21, we found that when
nanospheres attach to the nanocube, unlike the free space case, the
fluorescence decay curve cannot be fitted by one only exponential function.
Multi-exponential decays are actually used. In the other words, there are
different kinds of decay for these nanoemitters, due to the complexity of this
hybrid plasmon system (nanocube, polymer, and distribution of nanosphere
may all influence the decay). Besides, the size of nanosphere is 50 nm,
considering the distribution of near-field on nanocube surface (e. g. see the
near-field calculated by FDTD simulation, Fig. 3.19.d), the lifetime decay in one
nanosphere is not uniform when it is on nanocube surface: some molecules
inside the sphere are affected by the Purcell effect while other ones are not
sensitive to the nanocube. However, in general, an interesting trend is
demonstrated: the polymer thickness on the nanocube surface plays a role as
spacer, resulting in an effective tunable distance between nanocube and
nanosphere. This is why we still can see a clear decrease of the lifetime when
the exposure dose decreases.
70
Fig. 3.21 different nanosphere lifetime decay when nanosphere attached on cube-polymer
system with different exposure dose.
3.4.3 Integration of QDs to the vicinity of nanocube
For such hybrid plasmonic emitters based on nanophotopolymerization, we

have also used semiconductor Quantum Dots (QDs, emission at 620 nm,
excited by 405 nm laser) instead of fluorescence nanospheres. In that case,
QDs are randomly distributed inside of photopolymerizable formulation in order
to trap them locally through local plasmonic photopolymerizarion. In that case,
it is difficult to control emitter-cube distance but the position of the quantum
emitters can be well controlled through the polymer position. While for the
nanosphere situation (Fig. 3.19), the polymer thickness plays a role as spacer
between nanosphere and nanocube, the QDs are located almost over the
whole polymer nanovolume. For example, as shown as Fig. 3.18.c, if we do a
photopolymerization with the incident light polarization parallel to diagonal axis
of cube, we obtain two polymer lobes at the corners of cube. Since QDs are
mixed into polymer formulation, they emit light from these two lobes when
excited. In other words, QDs are all located at hot spots of the near-field
plasmon of nanocube. Taking advantage of this clear selective position at the
cube vicinity, and the resulting anisotropy of the active medium, one could
selectively excite the QDs by controlling the incident light polarization.
71
Considering this hybrid plasmon emission system, which has two polymer lobes
containing QDs along the diagonal corners, when the polarization orientation of
incident excitation light is parallel to the diagonal has QDs, a clear fluorescence
signal can be observed from this system. One the other hand, for incident
polarization perpendicular to the diagonal has QDs, due to the energy hot spot
is at the corner without QDs, weak fluorescence signal is expected. As a result,
we found two clear different emission states for these two different polarization
(Fig. 3.22).
Fig. 3. 22 Switchable hybrid plasmon-emitter [14]: a) SEM image of the hybrid plasmon
nanostructure, red arrow indicates the polarization of exposure used for plasmonic
photopolymerization; b) far-field fluorescence image for incident excitation polarization at
72
; exc=405 nm c) fluorescence spectrum of image b); d) fluorescence intensity as a
function of the angle of polarization of the excitation field at exc=405 nm. The blue arrows
indicate two specific states when incident excitation polarization is either parallel or
perpendicular to the diagonal axis with lobes; e).f) FDTD calculation for incident excitation
field at exc=405 nm for these two states. The black contour represents the integrated
polymer nanoparts that contain QDs.
Furthermore, this switchable hybrid plasmon-emitter could be extended to

single photon regime [14]. By decreasing the concentration of QDs in the
photopolymerization formulation, we could obtain a hybrid structure with only
one or few QDs inside the polymer lobes at cube corners. Fig. 3.23.a shows an
AFM image of such a hybrid plasmon-emitter. The original nanocube is diagonal
parallel to X-axis, leading to polymer lobes along X-axis after polymerization
using horizontal polarized exposure light. A pulsed laser of 405 nm with incident
polarization parallel to the polymer lobe along the X-axis is used for
fluorescence exciting. The corresponding fluorescent spectrum is obtained
using the Hanbury Brown-Twiss system [29] coupled with a confocal scanning
system that is sensitive to single quantum emitter emission, by which both
single-photon counting and spectral measurement can be achieved. We can
see a clear blinking from Fig.3.23.b and Fig.3.23.c, which is the signature of a
single (or few) QDs emission. In Figure Fig.3.23.b, this emission gets switched
off when the incident polarization is rotated to vertical polarized (using a half-
wave plate) due to the sudden lack of overlap between the exciting near-field
and the single QD. Autocorrelation function g(2) measurement [30] is performed
in order to determine the photon emission regime. We found that at a zero delay,
g(2)(0) 0.35 (Figure 3.23.d), which is below 0.5, illustrating there is only
single-photon emitted at the same time. This represents a first demonstration
of a polarization-driven switchable single photon emission. We also measured
the Purcell effect owing to the weak coupling between the trapped single QD
and the gold nanocube. We use a 5 MHz repetition rate pulsed laser for IRF
and lifetime measurement and obtained an IRF of about 0.63 ns. Several typical
hybrid nano-emitters are been measured, their lifetime decay are presented in
Fig.3.23.e. The typical lifetime of hybrid nano-emitter is 0.725 ns, while the
lifetime of single QDs in polymer was measured to be around 17.5 ns (Fig.
3.23.f). These measurements correspond to an averaged Purcell factor of
17.5/0.725 23. Here, the measurement of lifetime of QDs trapped in hybrid
nanostructure is restricted by our TCSPC system's time resolution. To conclude,
such a hybrid plasmon-emitter is possible to operate as a polarization
switchable single photon source, which plays a key role in quantum information
sciences [31].
73
Fig. 3.23 Hybrid plasmon-emitters in single photon regime. a) AFM image of nanocube
based hybrid plasmon-emitters, single or few QD contained in the polymer lobes; b), c)
fluorescent spectrum trace with incident light of vertical linear polarization at 405 nm. In b)
at 32 s, the polarization direction is rotated to vertical. d) g(2) measurement showing g(2)(0)
= 0.35. e) lifetime decay of three different hybrid plasmon-emitters containing single or few
QD. f) lifetime comparison between QD in polymer and QD in the vicinity of gold nanocube.
74
3.5 Summary
In this chapter, we have reported our attempt to attach few emitters to a polymer
probe, with the initial purpose to fabricate an active SNOM probe. First of all,
we have been building an optical system. This optical set-up is not only used to
monitor the attachment process, but also can be used to collect signal for
SNOM test, and make possible crucial characterizations including
spectroscopy and time resolved photoluminescence. Then we have integrated
50 nm single fluorescence polystyrene nanosphere to the extremity of polymer
probe on fiber end, by controlling functionalized probe touching single
nanosphere on glass substrate. Though the nanosphere is not located at the
very center of probe, it is still possible to use an active probe. This active probe
will be used to scan metal nanostructures, more interesting results will be
discussed at chapter 4. We also tried to locate the nanosphere to the center of
probe by new attachment method with an extra functionalized polymer tip. We
successfully locate 200 nm nanosphere to the center of probe. However, we
did not get good result for 50 nm nanospheres.
Relying on our experience, we succeeded in attaching nano-emitters to gold

nanocubes on a glass substrate. By using fluorescent nanospheres, we studied
its distance to the nanocube. This distance is related to the polymer thickness
that depends on the exposure dose used for fabricating the hybrid system by
plasmon 2-photon polymerization. Finally, we also reported an approach using
light emitting semiconductor QDs mixed within the photopolymerizable
formulation: a polarization-sensitive switchable hybrid plasmonic nano-emitter
has been developed.
75
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78
Chapter 4 Investigating nanostructures by using new
polymer probe
In this chapter, we will discuss the experiment of scanning on nanostructures

by using our polymer probe. First, we use the bare polymer probe, without
emitters, to scan on silver nanowires, in order to study surface plasmons
propagating on the nanowires. Then, by using the active probes described in
chapter 3, we have scanned on gold nanocube, to study the fluorescence profile
and photoluminescence that is characteristic of local light-matter interaction.
4.1 Scanning on silver nanowires by using bare polymer probe
In this section, we study light-matter interaction at silver nanowires (Ag-NW),

by detecting the optical near-field picked up by the bare polymer probe
scanning on the nanowire. Metal nanowires can support propagative surface
plasmons (SPs) that can be launched and detected at the extremities with high
numerical aperture objective lens [1][2][3]. When the polymer probe scans on
Ag-NW, because the radius of probe extremity is close to the diameter of the
NW, and the working scanning distance is less than 20 nm, the evanescent field
of the propagative SPs could couple into the probe, resulting in partial near-
fiel/far-field conversion. Then the produced far field is guided by both the
polymer tip and the optical fiber and can be detected [4].
4.1.1 Sample preparation
The Ag-NWs (Sigma-Aldrich, ref. 739448) were diluted in isopropanol solution.

These NWs have a length from 5 to 50 m, and a diameter of 115 nm. The
sample were prepared by spin coating the solution of Ag-NWs on glass
substrate at 3000 rpm for 30 s. From SEM image (Fig. 4.1), we can see the
smooth defect-free surface and faceted end of NW, as it is chemically grown,
resulting in a monocrystalline structure.
79
Fig.4. 1 SEM image of silver nanowire
On our SNOM stage, we first scan the sample to find the position of NWs by
the reflection confocal system (see Chapter.2), and to select a good NW for the
experiment. Because the SP propagation length of a NWs is always smaller
than 10 m [4][5], we have to choose a short and straight NW, so that we can
easily monitor the propagative SP from the scattering of NW extremity [3][6]. By
placing the extremity of NW at the focus point of laser by high numerical
objective lens, and adjusting the polarization direction, SP excitation/launching
can be clearly observed through scattering the other end of NW extremity [1][7].
The configuration used is shown at Fig. 4.2.
Fig.4. 2 Surface plasmon excitation by high numerical objective lens from NW extremity
[7].
80
It should be stressed that, for plasmon excitation, the polarization of incident
light has to be parallel to the NW axis (Fig.4.3.b), while the light whose
polarization perpendicular to the NW axis cannot excite the SP (Fig.4.3.c). This
observation is in agreement with the fact that a surface plasmons in transverse
magnetic (TM) longitudinal surface wave [3]. Actually, except this TM0 mode, a
hybrid mode (HE1) might be excited perpendicular polarization incident light in
some nanowires [8][9]. However, when the diameter of sliver nanowire is
smaller than 160 nm, the damping of the HE 1 mode during propagation in
nanowire is much fast than TM0 mode [10]. Therefore, for this case, diameter
of nanowire is 115 nm, only TM0 mode is observed.
a b c
Fig.4. 3 Lauching surface plasmons from the extremity of silver nanowire, a) nanowire
observed by camera; b) SP excited when polarization orientation of incident light parallel
to nanowire; c) no clear SP is excited when polarization orientation of the incident light is
perpendicular to the nanowire.
4.1.2 Observing surface plasmon by probe
After the SP is excited, the polymer probe integrated on optical fiber is

approached to the sample with the scanning head. After landing through shear-
force regulation (see Chap 2), the probe scans the whole NW, to collect both
the topography and the optical near field signal from the NW surface. Here the
sample does not move, to maintain the excitation of SP on nanowire, while the
probe scans on the nanowire. The signal is collected by the transmission light
path through probe and optical fiber (see Fig. 3.1, chapter 3). Figure 4.4 shows
a typical near-field analysis.
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a b c
Fig. 4.4 scanning image of the SP on nanowire, a) topography image of the nanowire; b)
near field optical signal collected from the nanowire surface by the polymer probe; c)
intensity curve at center of the optical image, along the red line shown in b).
From the topography image (Fig. 4.3.a), we can see the length of this NW is
4.2 m. The optical signal is from the transmission light path of the SNOM
system, showing the near field SP signal on the sample surface (Fig. 4.3.b).
The intensity in the image suddenly decreases, this is because here the
intensity of incident light decreases by 16 times manually, to protect the detector
out of saturation.
The SP intensity is damping exponentially during propagation along nanowire,

described as the follow equation,
(Eq.4.1)
is the surface plasmon propagation length, d is the propagating distance.

From this equation, we fit the intensity curve with an exponential function, we
find (see Fig.4.5). However, typical SP propagation length for
silver nanowire for green light is more than 1 µm [11]. Such a significant
decrease of SP propagation length is possibly due to surface roughness or
silver sulfide at silver nanowire surface [12][13]. Firstly, we could rule out the
influence from surface roughness since this nanowire is chemically synthesized
(see from the SEM image Fig.4.1). For the effect of silver sulfide covering layer,
our colleague Aurélie Broussier has comprehensively discussed in her article
and verified by a FDTD simulation [14]. In this article, it has been pointed out
that a 3 nm thick sulfur layer (see Fig. 4.6.b) on silver nanowire of 115 nm
diameter leads to , for an incident light at 514 nm. When the
thickness of sulfur layer increases to 4 nm, the drops to 400 nm.
Therefore, in our case, we can deduce a sulfur layer about several nanometer
covering the silver nanowire because of sulfurization.
82
Fig.4. 5 Exponential fit for intensity curve along the nanowire surface
Glass Silver
a b
Silver Sulfide
Ag
Glass
Fig.4. 6 a) Geometry of simulation about silver wire on glass substrate. b) Side view of the
geometry, silver wire is covered by silver sulfide layer and placed on glass substrate.
We also notice that the intensity curve of SP presents periodic oscillation,

looking like a beating stripe. For such a stripe, some article proved these
patterns are from the modulation of surface plasmon due to the plasmon
reflection by the distal wire end face [6][15][16]. The wire would thus act as a
Fabry-Perot cavity. However, in these articles, long SP propagation length
83
(more than 10 µm) is prerequisite, to guarantee a significant reflection plasmon
energy for modulation. In our case, the SP propagation length (475 nm) is
significantly shorter than the length of the nanowire, it thus is hard to consider
a light modulation resulting from SP reflection and interference. The fringe here
is more likely from the interference between incident excitation light and the
excited SP on nanowire surface. A part of the incident wave is scattered by the
wire extremity and generate a continuum of wavevectors, including a grazing
wavevectors that propagates in air parallel to the wire. It can reach the extremity
of the probe and be detected simultaneously to the SP and interfere with it (see
Fig.4.7)
Fig.4. 7 Schematic representation of the interference configuration
These two waves have different wave vectors during propagation, which leads
to a phase difference resulting in deterministic interference at the probe
extremity (position x) and intensity modulation along the wire during scanning.
We have the formula for both waves (ksp stands for the real part of the SP wave
vector):
(Eq.4.2)
(Eq.4.3)
Considering the properties of SP, we have:
(Eq.4.4)
(Eq.4.5)
84
To calculate the coherent superposition of these two waves, we have:
(Eq.4.6)
Now the intensity of superposition wave is
(Eq.4.7)
Therefore, we find the superposition wave has two modulation spatial

frequencies, shows an optical beat as an interference pattern. The lower spatial
frequency cosine term is an envelope the higher one, its amplitude is modulated.
We consider the period (242 nm) of pattern we observed in experiment as the
high modulation spatial frequency, because it is almost half of the wavelength
of incident excitation light. And since the SP decays very fast, it is unlikely to
observe lower spatial frequency pattern in this experiment. Therefore, for the
interference pattern period d, we have
(Eq.4.8)
With , we can deduce the wavelength and effective index of SP:
(Eq.4.9)
(Eq.4.10)
In this measurement, because the polymer probe can collect both evanescent
field and far field signal, we actually observed the superposition of SP wave and
scattered excitation wave. Therefore, for clear near-field imaging, it is important
to eliminate the background signal during detection. This is why the nanoemitter
as local light source is necessary for active probe, since the background
85
excitation light can be removed by spectral filtering.
4.2 Scanning on gold nanocube by using active probe
In this section, we will study gold nanocubes (used at chapter 3) by using active
probe. Single nanocubes (130 nm size) can be studied by depositing low
concentration of nanocube colloid solution on glass substrate. The light-matter
interaction between emitter and nanocube might be detected both by reflection
light path through the objective and the transmission path through the probe.
The active probe is fabricated by approaching the single 50 nm fluorescence
sphere on glass substrate with functionalized polymer probe surface (Fig. 3.11).
This polymer probe has a radius of 200 nm, and with a 50 nm fluorescence
nanosphere on its extremity. The Fabrication process of this active probe has
been introduced in Chapter 3. After landing the probe on sample substrate,
we use different excitation configuration and scanning mode (probe scanning
or sample stage scanning) to do the test. Meanwhile, time-resolved
photoluminescence measurement is carried out during scanning to discuss the
evolution of the fluorescence lifetime with the presence of the cube.
86
4.2.1 Characterization of nanocube and active probe
5
2
Fig. .4. 8 Scanning confocal image of five nanocubes on a glass substrate
Before probe landing, scanning confocal image of nanocubes on glass

substrate is measured from the reflection light path, as shown in Fig. 4.8. This
image mode has been introduced in chapter 3. No spectral filters are used in
this test, therefore, the signal we detected results from the scattering of the
incident 530 nm laser by the nanocubes. This confocal image helps us to find
the position of each nanocube. Because the size of cube in this experiment is
130 nm, smaller than the resolution of the observation system (230 nm), each
bright spot we see in this image cannot reveal the actual lateral shape of the
cube but rather the shape of the incident laser spot. This image shows the
scattering field of the nanocubes. However, if we change the polarization
orientation of the incident light, we observe a different image (Fig. 4.9). This is
because the local plasmonic enhancement of metal nanocube (Fig.4.10), which
is highly sensitive to the incident light polarization orientation, and leads to the
elongation of spot that we obtain on the far-field confocal image.
87
Fig.4. 9 Confocal scanning image of cube2 in Fig.4.8 with different polarization orientation
of incident light.
Fig.4. 10 a) FDTD calculation of Near-field intensity distribution of nanocube when the

incident light has a horizontal polarization, the intensity represents the enhancement factor
of local field intensity; b) Near-field decay as a function of distance from metal surface by
the data of (a), fitting with single exponential function.
After the active probe has landed at sample surface, same as Chapter 3, we
have to move the probe to bottom illumination laser spot, in order to align
reflection light path and transmission light path (see Fig. 3.1). From
transmission light path, 530 nm laser is coupled into the fiber, and then
propagates to the probe extremity. When we scan the probe on an empty area
of the glass substrate, from reflection light path, we can observe the light
propagates through the probe and the spot indicates the position of the probe
(Fig.4.11.a). If we add a spectral filter before detector and scan the probe as
the same area as former image, we can get a fluorescence spot image from the
probe at = 603 nm (Fig. 4.11.b). This fluorescence emission is from
nanosphere attached on probe and we can find the fluorescence spot is not at
the same position of 530 nm spot from probe extremity at former image. There
is a spatial shift of about 200 nm between the 530 nm spot from probe extremity
and the 603 nm fluorescence spot from the nanosphere. This spatial shift is in
88
agreement with that observed in the SEM image Fig. 3.11, chapter 3.
Since the active probe would be used for scanning single nanocube, expecting
a stable fluorescence emission as well as a highest fluorescence signal
intensity, we prefer to align the nanosphere to the position of bottom illumination
laser spot rather than the center of probe extremity. Considering bottom exciting
and sample scanning, Fig.4.12 illustrates the relative size and position of the
polymer probe, the nanosphere and the nanocube. The surface of polymer
probe has been approximated by a parabola, with curvature of 200 nm at
bottom. The nanosphere therefore locates at the surface of polymer probe 200
nm away from the center.
a b
Fig 4. 11 a) illumination from the probe at the sample surface at =530 nm. b) fluorescence
image at =603 nm from the probe, due to the fluorescence nanosphere on probe (same
illumination as for a))
89
Polyme
rProbe
nanospher
Gold
nanocube
Illuminatio
n laser
Fig.4. 12 schematic of polymer probe with nanosphere and nanocube (unit: m)
4.2.2 Fluorescence imaging with excitation from bottom and sample
scanning
We first recorded scanning fluorescence image as well as the simultaneous

topography image by scanning the sample (Fig. 4.13). As described above, the
nanosphere on probe is been aligned to the bottom illumination laser spot. This
530 nm incident laser excites the nanosphere on probe, the active nanosphere
then becomes a local fluorescence light source at 603 nm. During sample
scanning, when nanocube interacts with the active probe, both scattering and
fluorescence are collected simultaneously from the bottom objective lens
in 4.13.a) and through the polymer probe optical
-pass filter at
both light path respectively. We also obtain the topography image (shear force
mode described in Chapter 2) of this nanocube at same time (Fig.4.13.d).
The schematic of probe configuration (Fig.4.12 and Fig.4.16) can help us

understand the obtained images. Because we use a constant height mode for
scanning, the topography image is a convolution of the surface of the active
90
polymer probe and the nanocube. From Fig.4.14, we can see a shoulder at the
right part, which corresponds the nanosphere location illustrated in Fig.4.12.
From Fig.4.13.a, We can see a weak shadow corresponding to the topography
image, a dark shadow at center and small bright spot close to the dark shadow,
which corresponds to the position of nanosphere (Fig.4.14, Fig.4.15). Fig.
4.13.b is zoomed image for the brightest spot at Fig.4.13.a, by reducing scan
area to 200 nm x 200 nm square.
a b
c d
Fig. 4.13 Sample scanning (with active probe landed) image of the gold nanocube: a)
fluorescence image from reflection light path; b) zoom of the bright part in image a); c)
fluorescence image from transmission light path; d) topography image of the cube,
simultaneous signal with reflection and transmission signal.
Fig. 4.14 Profile along the red line of the topography image of the nanocube probed by the
polymer tip (Fig. 4.11.d)
91
Fig.4. 15 Profile along the red line of the fluorescence reflection image with the active
probe above the scanned nanocube (Fig. 4.11.a).
Because the nanosphere is aligned at the position of incident excitation laser

spot (Fig. 4.12), the nanosphere is always activated before the probe meets the
nanocube during scanning, which leads to bright background at Fig.4.13.a.
When the nanocube approaches to the probe (Fig. 4.16.b), one edge of the
nanocube will firstly contact the probe surface, and the probe will lift along with
the probe surface profile, thus nanosphere will also lift from the focus point of
excitation laser spot, and the fluorescence intensity will decrease along with the
distant of nanosphere away from focus point, resulting in a the weak shadow
from the image. When the probe scan to the top of nanocube, because it is the
highest position of the cube, the nanosphere is also at the farthest position to
the focus point, thus it emits weakest fluorescence intensity. Meanwhile, at
near-field region, the local field is only enhanced at the surface of nanocube
along polarization orientation of incident light, when the nanosphere is at the
top of nanocube, excitation laser from bottom will be blocked. This is why the
dark shadow area appears.
Once the nanosphere moves from top to the edge of nanocube, the nanosphere
is approaching the enhanced near-field of nanocube (Fig.4.16.d), thus the
fluorescence intensity increases, showing a bright spot close to the dark
shadow (Fig.4.15). Thanks to the near-field enhancement of nanocube, the
fluorescence intensity gets amplified clearly. From Fig. 4.15 we can see at the
bright spot the fluorescence intensity is 500, while free space intensity is 350.
And we take darkest part of the curve as a background signal, therefore, the
fluorescence intensity is amplified by around 1.5 times when the nanosphere
touches the edge of nanocube. It should be noticed that the resolution of our
confocal system is 230 nm, while this scanning fluorescence image has a better
the resolution and, in the other word, breaks the diffraction limit. In Fig. 4.13.b,
the size of this spot is about 40 nm, corresponds to the nanosphere size 50 nm.
92
a b
c d
Fig.4. 16 Nanocube at different position during sample scanning when the active probe
landing on: a) probe landing on substrate; b) one edge of nanocube contact probe surface;
c) nanosphere on the top of nanocube; d) nanosphere on the edge of nanocube.
Fig. 4.13.c shows the transmission fluorescence scanning image. This

transmission signal is collected by the probe and propagates through the fiber
to detector. Unfortunately, because of the delocalization of the nanosphere
relative to the probe center, the probe cannot collect the florescence signal very
well, we can only see a very weak shadow at the image. There is no more
interesting information from the transmission fluorescence image due to low
signal. The nanosphere has to be precisely aligned to the center of probe, if we
want to have a good transmission fluorescence image in this configuration.
These above results prove one thing: from the reflection light path, we can
obtain some part of near-field distribution at nanocube surface, however, this
near-field image is actually from the fluorescence signal excited by local field,
because only one edge of the nanocube is possible to contact with nanosphere,
only the local field of this edge might be observed. It should be pointed out that
the local field of nanocube is highly sensitive to polarization direction of incident
light, we can study the change of local field on one edge of nanocube when
polarization direction of incident light changes. Fig.4.17 shows the result of
experiment, the fluorescent image by reflection light path for the cube 5 from
Fig. 4.8. To observe easily, the brightness and contrast of these image have
been modified. When the polarization direction changes from vertical to
horizontal, the bright spot close to the dark shadow moves from lower half of
93
the edge (4.17.a) to the upper half (Fig.4.17.b).
a b
E E
Fig.4. 17 fluorescence image from reflection light path, with different polarization direction
of incident excitation light: a) vertical polarization; b) horizontal polarization.
This is because the enhanced local field on this edge changes from lower half
to upper half when the polarization direction changes. Fig.4.18 shows the FDTD
calculation of local near-field at vicinity nanocube with different polarization
direction of incident excitation light (530 nm). According to the dark shadow in
square. For Fig.4.18.a, when the incident light polarization is vertical, at the
right edge, the hot spot locates at the lower half, while for Fig.4.18.b, when the
polarization is horizontal, the hot spot locates at the upper half. And this
simulation explains the experiment result at Fig.4.17. Therefore, once the
fluorescence nanosphere contacts with nanocube, the fluorescence image can
represent near-field at nanocube vicinity, in this experiment, only the near-field
of one edge of cube can be observed. For better imaging, in the other word,
obtain more near-field information, it is necessary to find a method for
nanoemitter contacting more parts of nanostructure, for example, to place the
nanosphere at the exact center of probe extremity.
a b
E E
Fig.4. 18 FDTD simulation of near-field at nanocube vicinity, by 530 nm excitation light with
94
different polarization direction: a) vertical polarization; b) horizontal polarization
4.2.3 Lifetime measurement when active probe scanning on single
nanocube
We can also study the lifetime decay for different emission situation. Fig. 4.19
is the normalized decay curve for different emission situation. The red curve is
the instrument response function (IRF) which indicates the resolution of the
system. We can notice that IRF is associated to a time resolution of about 0.6
ns. Green curve is the emission from nanosphere on glass substrate, if we fit
this curve by exponential function, will have the lifetime decay for a nanosphere
is 6.3ns. Black curve is the emission from nanosphere attached on polymer
probe, and landing to the glass substrate (Fig. 4.16.a), whose lifetime decay
can be fit to 4.3 ns, due to change of environment refractive index by the
presence of polymer probe. The blue curve is the life time measurement when
the nanosphere probe scans on the edge of nanocube (Fig. 4.16.d), which has
a very short decay close or less than the IRF (0.6ns). This significant decrease
of lifetime decay from free space to vicinity of nanocube is the signature of a
significant Purcell effect for this metal nanostructure, which means the gold
nanocube has a rich local density of state that acts as channel of desexcitation
of the molecules within the spheres [5,17]. The achieved Purcell factor is higher
than 6.3/0.6 = 10.5.
If we compare data of Fig. 4.19 with the results of chapter 3 (Fig. 3.19) with the
nanospheres attached on the nanocube surface, we notice that lifetime is
generally weaker in Fig. 4.19. If we more particularly consider the smallest
lifetime in Fig. 3.19: the polymer spacer resulting from an exposure dose of 40%
Dth is less than 20 nm (see Fig. 4. 20 as a reminder), which also corresponds,
for Fig. 4.19 to the scanning probe working distance that we discussed at
Chapter 2.
95
Fig.4. 19 Lifetime decay for different emission situation
Fig.4. 20 Different polymer size when using different exposure dose (percentage of Dth) to
do a local photopolyermization on nanocube.
96
4.3 Summary
In this chapter, we introduced different uses of our new polymer probe. First,
we used the bare polymer as a near-field probe for scanning on a silver
nanowire whose one extremity is illuminated by a focused beam, for plasmon
launching. We observed the superposition of surface plasmon and excitation
field on nanowire because the probe collected both the near-field evanescent
wave and the far-field wave. Then we used the active probe fabricated at
Chapter 3 to study single gold nanocube. Although the localization of the
fluorescent nanosphere on the probe highly influences the observation, we
obtained a high-resolution fluorescence image corresponding to the nanocube
profile and breaking the diffraction limit. We also measured the change in the
fluorescence lifetime when the active probe scans on the nanocube, showing a
Purcell factor close to 10. Additionally, by comparison with the result from
Chapter 3.4.2, we assessed the sample-probe working distance for our shear-
force feedback loop scanning system.
97
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99
Conclusion
In this thesis, we have presented a contribution to the technique of SNOM, by

working on an idea of active SNOM probe based on polymer-tipped optical
fibers. The work of SNOM is mainly focusing on near-field imaging, and obtain
high spatial frequency information of optical field, as a result, to break diffraction
limit during observation. For SNOM measurement, the probe plays a key role.
We have worked on a new concept of hybrid active probe to meet the
requirements of experiment.
Our goal was to fabricate an optical probe for scanning in the near-field regime,
with a local light source at its extremity. We firstly fabricated a polymer tip on
the extremity of optical fiber by photopolymerization. This light-induced polymer
tip is a reproduction of propagating field emerging from the fiber. Therefore, this
tip can enable a good optical field confinement. The parameters of
polymerization have been optimized, so that we can obtain a suitable micro
polymer probe for scanning on sub-wavelength nanostructures. During the
thesis, we have worked on the adaptation of the fiber with polymer probe to use
it with a scanning probe commercial head. The probe has been glued on a
tuning fork head and we demonstrated its use as a local probe using shear-
force method for probe-sample distance controlling.
Then we have worked on the integration of a few nano-emitters at the extremity

of polymer probe in order to get an active probe for SNOM.
First of all, an optical system was built for monitoring fabrication of active as
well as for SNOM measurement. The optical set-up is coupled to the tuning fork
head for enabling both optical excitation and detection. In particular,
spectroscopic and life time measurements are now possible.
Two strategies of emitter attachment have been tested. One consists of a
surface functionalization of the whole polymer probe for grasping emitters from
a glass substrate. The other one aims at functionalizing specific area on the
polymer probe for attaching emitters from colloid emitter solution where the
probe is immerged. Two kinds of nano-emitters have been considered: doped
fluorescent polystyrene nanospheres and semiconducting Quantum Dots. After
numerous tests, we finally obtained an active probe with 50-nm fluorescent
nanosphere on the surface of extremity of the polymer probe, though the
nanosphere is, in general, not located at the very center of probe extremity.
Importantly, the attachment strategies under investigation have been used on

nanocubes deposited on glass substrate, in order to develop new hybrid
plasmon nano-emitters. Here the polymer is locally photo-patterned through
plasmons-induced polymerization using the plasmonic modes of the gold
nanocube. With fluorescent nanospheres attached to the polymer, anf thus
100
placed in the close vicinity of the
lifetime (induced by the Purcell effect) as a function of its distance to the
nanocube. This distance is controlled via the thickness of the polymer deposited
by plasmonic photopolymerization. Light-emitting semiconductor QDs have
been considered too. A polarization-sensitive switchable hybrid plasmonic
nano-emitter has been developed, and been further extended to the single
photon regime.
The use of the polymer probe has been tested on two samples. First, a silver
nanowire with plasmon launched from its extremity was scanned by a bare
polymer probe. The probe collected the whole field from sample surface (both
Surface Plasmon wave and excitation wave), therefore, we obtained a
superposition of optical information of near-field and far-field from sample and
were able to get information about the surface plasmon polariton supported by
the silver nanowire. Then we used the active probe to study single gold
nanocube. Although the localization of the fluorescent nanosphere on the probe
highly influences the observation, near-field information of nanocube has been
partly obtained. The near-field imaging enabled a high-resolution fluorescence
image corresponding to the nanocube profile and breaking the diffraction limit.
We also measured the change in the fluorescence lifetime of the active probe
due to the presence of metallic nanostructure when the active probe scans on
the nanocube, showing a Purcell factor close to 10. Meanwhile, by comparison
with the result of study about lifetime changes of different distances between
from emitter and metallic nanostructure from Chapter 3, we assessed the
effective sample-probe working distance for our shear-force feedback loop
scanning system.
For further research, more configuration can be possibly considered. For

example, Nitrogen-Vacancy center can be also used as nano-emitter for active
probe, leading to single photon test. Besides, we can also replace fluorescent
emitter by some metal nanoparticle, when metal nanoparticle acts as probe.
We could exploit the gap mode between nanoparticle and sample structure,
resulting in a significantly enhanced near-field.
Apart from SNOM experiment, taking advantage of the high energy
confinement of such a probe, other application like optical tweezers is also
conceivable.
101
Annex
Résumé en Français
1 Introduction
Dans le cas de l'imagerie optique traditionnelle en champ lointain, la résolution de

l'imagerie est limitée par la limite de diffraction [1][2]. L'idée de la microscopie optique en
champ proche à balayage (Scanning Near-field Optical Microscopy, SNOM) est de
dépasser la limite de diffraction par l'imagerie en champ proche, qui est « transportée » via
des champs évanescents à décroissance exponentielle [3-5].
Pour le SNOM classique, il possède une sonde avec un trou de sous-longueur d'onde au
sommet balayant l'échantillon tout en maintenant une distance sonde-échantillon de
quelques nanomètres. Par conséquent, un système SNOM typique est une combinaison
de la microscopie optique et de la microscopie à sonde à balayage (SPM). Les chercheurs
utilisent souvent une fibre optique conique [6] ou une pointe nano-métal [7-9] comme
pointe de sonde pour SNOM. Alors que le système SPM promet que la sonde fonctionne
dans une zone de champ proche de sous-longueur d'onde, puisque les ondes
évanescentes se désintègrent de manière exponentielle.
Diffusion de la lumière à partir d'un objet arbitraire une superposition d'ondes planes et
d'ondes évanescentes. Parce que les ondes évanescentes sont en décroissance
exponentielle, seules les ondes planes peuvent être collectées par un détecteur de champ
lointain. Cependant, les informations de grandes fréquences spéciales sont associées aux
ondes évanescentes, les ondes planes à champ lointain ont une limitation de fréquence
spéciale. Cette limitation correspond à la limitation de diffraction à l'observation en champ
lointain, qui impose la limite de résolution d'imagerie. C'est pourquoi nous nous intéressons
au signal en champ proche. Avec la microscopie en champ proche, nous pouvons collecter
des informations de grande fréquence spatiale en champ proche en diffusant des ondes
évanescentes vers des ondes planes de propagation en champ lointain.
Dans cette thèse, nous essayons de développer une nouvelle sonde SNOM active avec
sonde polymère et nanoémetteurs. La sonde est photopolymérisée à l'extrémité de la fibre
et utilise la méthode de la force de cisaillement du diapason pour contrôler la distance
sonde-échantillon. Contrairement à la fibre optique conique traditionnelle fabriquée par des
techniques de tirage ou de gravure, la sonde fabriquée par photopolymérisation a un
meilleur confinement de champ car la modélisation du polymère déclenché par la lumière
est une reproduction du champ de propagation. D'autre part, la rigidité du polymère est
bien inférieure à celle de la silice (utilisée pour la fibre optique) ou du métal, ce qui pose
un grand défi pour le contrôle de la distance sonde-échantillon.
Pour l'illumination locale de la sonde, nous essayons d'utiliser des nanoémetteurs
active. Selon Bethe-Bouwkamp-Theory, l'émission d'une petite ouverture équivaut à un

dipôle électrique et magnétique situé à la position de l'ouverture [10]. Ainsi, les
nanoémetteurs peuvent agir comme des émetteurs locaux. Le signal fluorescent est filtré
à partir d'un signal d'excitation important à l'aide d'un filtre passe-bande. Au lieu de la taille
d'ouverture, la taille du nanoémetteur définit la fréquence spatiale la plus grande du signal
détectable.
Nous utiliserons cette sonde active pour étudier des nanostructures plasmoniques, des
nanofils d'argent [11] et des nanocubes d'or [12] sont testés et analysés. Les
nanostructures plasmoniques peuvent avoir un bon confinement des champs lumineux à
proximité, ce qui conduit à un fort signal de champ proche. Pour les nanofils, on observe
la propagation du polariton de plasmon de surface (SPP) le long du fil. Pour le nanocube,
le renforcement de la fluorescence en champ proche causée par la résonance
plasmonique de surface localisée (LSPR) est détectée. En attendant, profitant du LSPR et
de la photopolymérisation, nous essayons de fabriquer un système hybride plasmon-
émetteur [13]. Lorsque nous utilisons des points quantiques comme émetteur pour le
système, il est possible de réaliser un système de plasmon couplé à un photon.
2 Photopolymérisation pour sonde polymère
2.1 Méthode de fabrication d'une pointe polymère sur la surface d'une
extrémité de fibre
Dans cette partie, nous présenterons comment fabriquer une micro sonde polymère sur
une extrémité de fibre optique, qui pourrait être utilisée comme sonde SNOM, et cette
sonde sera ensuite traitée pour devenir une sonde active. La méthode de fabrication que
nous utilisons est basée sur la photopolymérisation. Nous photopolymérisons une sonde
polymère sur la surface de l'extrémité de la fibre. Cette sonde agit comme une sonde
mécanique à balayage fournissant des informations de topographie de la surface de
l'échantillon. Pendant ce temps, il peut collecter le signal optique en champ proche pendant
le balayage. Pour SNOM, nous utilisons le mode force de cisaillement pour contrôler la
distance sonde-échantillon pendant le balayage.
La photopolymérisation est une méthode bien connue et bien développée pour la

fabrication de micro et nanostructures 3D [14,15]. Au cours d'un processus de
photopolymérisation, la formulation liquide est exposée à la lumière, après absorption de
l'énergie des photons, la polymérisation se produit, de sorte que les monomères de la
formulation se combinent, ce qui entraîne le durcissement du matériau. Techniquement,
2
on utilise le laser pour déclencher la réaction de polymérisation, lorsque la lumière se
propage à travers la formulation polymère, une fois l'intensité du laser incident au-dessus
du seuil de polymérisation, le processus de durcissement démarre. En conséquence, la
structure photopolymérisée est une reproduction du champ optique se propageant.
Fig. 1 Espèces chimiques contenues dans la formulation photopolymérisable a) PETA

(triacrylate de pentaérythritol) ; b) IRG819
Une formulation typique est le PETA (triacrylate de pentaérythritol) (Fig.1.a), avec

IRGACURE 819 (Fig.1.b) comme photoinitiateur. IRG819 est un photoinitiateur polyvalent
pour la polymérisation radicalaire de résines insaturées lors d'une exposition à la lumière
UV. Cependant, utilisé comme sonde à balayage, la rigidité du polymère est importante.
Grâce à un collègue (Borui Li) de notre groupe et des collègues de Mulhouse, en ajoutant
plusieurs initiateurs dans la formulation de polymérisation, un réseau de polymères
interpénétrants (IPN) peut apparaître lors de la polymérisation [16][17]. L'IPN est le
polymère comprenant deux ou plusieurs réseaux entrelacés mais non liés de manière
covalente. L'augmentation de la complexité spéciale confère une densité de réticulation
plus élevée. Pour la formulation IPN, son module de Young est d'environ 8 GPa, une assez
bonne rigidité parmi les polymères.
La configuration utilisée pour la polymérisation à l'extrémité de la fibre est illustrée à la

Fig.2. Il se compose d'un système de couplage d'un faisceau laser à travers la fibre, une
caméra avec objectif pour le suivi de l'expérience et d'une platine de contrôle de la position
de la fibre optique. Pour la fibre, nous choisissons le s-405xp de Thorlabs, qui prend en
charge la propagation de la lumière monomode de 400 nm à 680 nm, couvrant ainsi
presque toute la gamme de longueurs d'onde de la lumière visible dans le régime
monomode.
3
Exposure laser been
coupled into fiber
fiber
Position stage
Camera Zoom tube lens
Formulation drop
Fig. 2 Schéma de configuration pour fabrication de la sonde polymère
Avant de faire la procédure d'exposition réelle sur la surface de l'extrémité de la fibre, nous
calculons le processus de polymérisation. Pour ce processus, nous utilisons le modèle et
le code FDTD (Finite Difference Time Domain) de Lumerical [18]. A l'extrémité de la fibre,
la lumière se propage à travers la formulation, une certaine énergie est absorbée. Une fois
que l'énergie dépasse le seuil de déclenchement, la polymérisation se produit, et l'indice
de réfraction change au niveau de la zone polymérisée, alors ce changement affecte la
propagation de la lumière, c'est-à-dire modifie le profil d'absorption.
Il s'agit donc d'un processus en constante évolution. Pour le calcul, un algorithme récursif
est
ofil d'absorption en fonction de l'indice
de réfraction simultanément, puis nous définissons un seuil pour l'intensité d'absorption
qui déclenche la polymérisation. L'indice de réfraction changera en raison de la
polymérisation, et cette nouvelle distribution d'indice de réfraction sera mise à jour pour le
Pour simuler l'expérience, nous définissons le paramètre comme la condition que nous
utilisons. La fibre est une fibre monomode, avec une gaine de 125 µm de diamètre et un
polymère est de 1,48 et après polymérisation, il passera à 1,52. Ici, le calcul est de 1 s, et
avec un intervalle de temps de 0,1 s, il exécutera 10 fois l'itération pour le calcul.
La Fig.3 montre la simulation de 10 itérations temporelles pour un temps d'exposition total

de 1 s. La rangée supérieure montre le changement d'indice de réfraction (la zone rouge
indique le matériau polymérisé) et la rangée inférieure montre l'intensité énergétique
lorsque la lumière se propage à travers cette pointe polymère. De ce calcul, on peut
remarquer que cette pointe polymère n'est pas un cône parfait. Lorsque la longueur de la
pointe est d'environ 10 µm, la pointe est constituée de deux parties : un grand cône de
base en bas et une pointe pointue en haut, et cette forme correspond assez bien au résultat
de l'expérience (illustré à la Fig.4) .
4
|E|^2, t=0.1s |E|^2, t=0.2s |E|^2, t=0.3s |E|^2, t=0.4s |E|^2, t=0.5s
Re(index), t=0.1s Re(index), t=0.2s Re(index), t=0.3s Re(index), t=0.4s Re(index), t=0.5s
|E|^2, t=0.6s |E|^2, t=0.7s |E|^2, t=0.8s |E|^2, t=0.9s |E|^2, t=1s
Re(index), t=0.6s Re(index), t=0.7s Re(index), t=0.8s Re(index), t=0.9s Re(index), t=1s
Fig. 3 Simulation pour une photopolymérisation de 1 s sur extrémité de fibre. Le temps

interne pour chaque image est de 0,1 s. La rangée supérieure montre la distribution
d'indice au-dessus de la surface d'extrémité de la fibre, et la rangée inférieure montre le
champ d'énergie lorsque la lumière se propage à travers la sonde polymère.
5
Fig. 4 Pointe en polymère fabriquée à partir d'une expérience réelle, nous pouvons voir la
pointe pointue en haut, correspondant au résultat de la simulation
Par ailleurs, on remarque quand la lumière se propage à travers la pointe, la distribution

de l'intensité énergétique n'est pas homogène. Lors de la propagation, l'énergie lumineuse
se concentre principalement sur la surface de l'extrémité de la fibre et la pointe effilée au
sommet. Pour une longue pointe en polymère, peu d'énergie lumineuse est concentrée
dans la partie médiane. Cette distribution d'énergie dans la pointe polymère peut influencer
sa propriété mécanique en tant que sonde à balayage. En effet, si on regarde les images
de la distribution d'indice, on remarque qu'une partie au milieu de la pointe ne présente
pas d'indice de réfraction maximum, ce qui signifie que cette partie n'est pas totalement
polymérisée. Et en raison de la distribution d'énergie, cette pièce ne pouvait pas absorber
suffisamment d'énergie même avec une post-exposition pour le renforcement. Pour
conclure, il est probable qu'une pointe polymère plus courte sans la "partie médiane faible"
puisse mieux répondre aux exigences d'une sonde à balayage.
Dans l'expérience réelle, tout d'abord, un laser à 405 nm est couplé dans la fibre
monomode. L'intensité de laser est détectée à l'extrémité de la fibre, pour savoir combien
d'énergie se propagera à travers l'extrémité clivée, et cela est considéré comme l'énergie
utilisée pour la photopolymérisation pour la sonde polymère à la surface de l'extrémité de
la fibre. Après réglage de l'énergie de déclenchement de la photopolymérisation, un
obturateur permet de contrôler le temps d'exposition de la photopolymérisation. L'extrémité
de la fibre est trempée dans une goutte de formulation photopolymérisable déposée sur
un substrat de verre (voir Fig.2). En conséquence, nous obtenons un hémisphère
recouvrant la surface d'extrémité de la fibre après que l'extrémité de la fibre est extraite de
la gouttelette. La taille de cet hémisphère est influencée par la tension superficielle entre
la formulation et la surface d'extrémité de fibre, qui définit le volume de la formulation sur
la surface d'extrémité de fibre. La hauteur de cet hémisphère est la limite de la longueur
de la pointe polymère dans cette configuration (Fig.4). Après régler le temps pour
l'exposition, nous pouvons ouvrir l'obturateur pour déclencher la photonpolymérisation sur
la surface d'extrémité de la fibre. Comme discuté dans le calcul, pendant la polymérisation,
6
le polymère se développera de l'extrémité de la fibre à une pointe conique. Après
exposition, l'extrémité de la fibre est immergée dans de l'acétone pour éliminer la
formulation non polymérisée. Pour s'assurer que l'ensemble de la pointe polymère a été
complètement polymérisé, une post-exposition aux UV est effectuée. La pointe polymère
est renforcée par l'étape de post-exposition.
100 µm
Fig. 5 Formulation de polymère hémisphérique sur la surface de l'extrémité de la fibre, filtre

passe-long (> 650 nm) utilisé pour la caméra pour éviter la polymérisation en éclairant la
lumière.
A l'extrémité de la fibre, le mode photonique a une distribution gaussienne. Pour un

faisceau gaussien, l'énergie est fortement confinée en son centre. Au cours de la
polymérisation, lorsque l'énergie du laser d'exposition diminue, la section transversale du
faisceau permettant une polymérisation efficace diminuera également. Montré à la Fig.6,
E0 est l'énergie seuil de déclenchement de la polymérisation, lorsque l'énergie laser
diminue de E1 à E2, la section transversale au seuil diminue de d1 à d2. En conséquence,
nous obtiendrons un rayon de pointe plus petit avec une énergie d'exposition plus petite.
A partir de ce principe, le plus petit rayon de pointe que nous pouvons fabriquer est de 100
nm, lorsque l'énergie d'exposition est de 600nw. D'autre part, lorsque l'intensité
d'exposition est fixe et que le temps d'exposition change, du fait que la section efficace du
seuil de polymérisation est également fixée par l'intensité d'exposition, le rayon de la pointe
polymère est alors maintenu; tandis que la longueur de la pointe en polymère augmente
avec le temps d'exposition. Pour conclure, dans cette expérience, le temps d'exposition
définit la longueur de la pointe de la sonde, et la puissance d'exposition définit le rayon de
la pointe. Une méthode pour limiter la longueur de la pointe avec un certain temps
d'exposition est diminuer le volume de la formulation à l'extrémité de la fibre. Nous pouvons
obtenir une gouttelette de formulation d'environ 2 µm de hauteur à l'extrémité de la fibre
(normalement la hauteur est environ 10 µm). La figure 7 montre une pointe en polymère
fabriquée par cette méthode. Il présente une longueur d'environ 2 µm, avec un rayon de
pointe d'environ 200 nm. Ainsi, on obtient une pointe courte avec un rayon relativement
faible. On utilisera préférentiellement de telles pointes en polymère comme sonde de
balayage.
7
E1
E2
d1 d2
Fig. 6 Énergie d'exposition supérieure au seuil de déclenchement de la polymérisation
Fig. 7 Pointe polymère fabriquée par une énergie d'exposition de 600 nw et un temps
d'exposition de 1/15 s tandis que le volume de gouttelettes de formulation a été diminué.
2.2 Pointe polymère utilisée comme sonde de balayage
Pour la mesure SNOM, il est nécessaire de positionner une sonde très près de la surface
de l'échantillon. La lumière diffusée résultant de l'interaction lumière-matière en champ
proche est collectée par le détecteur via la sonde. Pour accéder à l'interaction lumière-
matière en champ proche, la distance sonde-échantillon doit être beaucoup plus petite que
8
la longueur d'onde de la lumière [19][20].
Par conséquent, nous avons besoin d'une boucle fermée de rétroaction pour contrôler le
distance sonde-échantillon pendant le balayage de la nanostructure (Fig.8). Nous utilisons
un système commercial de NTMDT comme de microscopie à sonde locale
(Scanning Probe Microscope, SPM) [21].
Setpoint + Controller Amplification

Tuning
fork
-
Fig. 8 Boucle de rétroaction pour la microscopie à sonde à balayage. Le « setpoint » est
défini en externe correspondant au signal d'interaction mesuré. Le contrôleur peut ajuster
la vitesse et la stabilité de réponse de la boucle de rétroaction.
Il existe plusieurs stratégies pour contrôler le distance sonde-échantillon pour SNOM[22-

26]. Dans notre expérience, nous utilisons la méthode bien connue de la force de
cisaillement [27]. La distance sonde-échantillon influence la vibration d'une sonde parallèle
à la surface de l'échantillon. La fibre avec sonde polymère est collée à un bras du diapason
(Fig.9). Lorsque la sonde oscille à la fréquence de résonance du diapason, l'amplitude, la
phase et la fréquence de l'oscillation sont mesurées (Fig.10), et tous ces paramètres
peuvent être utilisés pour la boucle fermée de rétroaction afin de contrôler la distance
sonde-échantillon [28]. La distance d'interaction de la force de cisaillement est d'environ 1
à 100 nm selon le type de sonde et d'échantillon, ainsi que les conditions ambiantes, y
compris l'humidité, la température et le niveau de vide [31,32]. Le distance d'interaction
indique la distance sonde-échantillon pendant le balayage [29][30].
Fig. 9 Fibre avec sonde en polymère collée sur le diapason, l'image de droite est le zoom
de la vue latérale du diapason.
9
Fig. 10 Amplitude d'oscillation et phase du diapason détecté sur notre système en fonction
de la fréquence à la fréquence de résonance.
Lorsque la distance sonde-échantillon diminue, l'extrémité de la fibre avec pointe polymère

se rapproche et interagit avec la surface de l'échantillon, ce qui entraîne le décalage de
fréquence de résonance et la chute du facteur Q, ainsi que la diminution de l'amplitude
d'oscillation. L'amplitude d'oscillation est proportionnelle au signal de tension provenant de
l'électrode à diapason (utilisée comme intensité de l'amplitude d'oscillation pour le système
de balayage).
Lorsque la sonde se rapproche de la surface de l'échantillon, une interaction se produit

entre la sonde et l'échantillon, ainsi une force de cisaillement dans le plan agit sur la sonde
et l'amplitude d'oscillation diminue à partir de la situation d'espace libre. Cette diminution
est détectée par le système de balayage grâce à une chute de tension. Avec une boucle
fermée de rétroaction, le système ajuste la distance entre la sonde et l'échantillon, pour
maintenir la tension d'amplitude d'oscillation à un "set point", donc, la sonde balaye avec
une force d'interaction constante, c'est-à-dire à une distance constante de l'échantillon
surface. Pour assurer le bon fonctionnement de ce système de contrôler le distance sonde-
échantillon par force de cisaillement, il est important que la sonde reste rigide pendant
balayage afin d'assurer un amortissement maximum du diapason. La condition à remplir
est que pendant balayage, l'amplitude de déformation de la sonde elle-même doit toujours
être inférieure à l'amplitude de déformation du diapason. Pour une sonde polymère utilisée
pour le balayage, il est important d'avoir une sonde rigide afin que la force de cisaillement
puisse être bien détectée par la configuration avec diapason. Pour un matériau donné,
nous devons fabriquer une sonde courte et épaisse pour garantir sa rigidité.
10
3 Attachement de quelques émetteurs de fluorescence sur sonde
polymère
3.1 Attachement d'un seul émetteur à partir d'un substrat en verre
Une bonne méthode d'observation optique est cruciale pour SNOM. Pour le traitement des
nanostructures et des émetteurs, les objets doivent être bien surveillés. Dans notre
expérience, le système d'observation optique est illustré à la Fig.11. Deux chemins
optiques ont été développées : la réflexion et la transmission. Le chemin de réflexion
collecte le signal réfléchi par l'échantillon, il peut fonctionner sans sonde. Dans ce cas, la
même lentille d'objectif est utilisée pour l'excitation de l'échantillon et la collecte de la
lumière. Avec la caméra et les détecteurs optiques, en utilisant ce chemin optique, nous
pouvons localiser et analyser l'échantillon avant que la sonde n'atterrisse sur la surface de
l'échantillon. Lorsque la sonde atterrit sur la surface de l'échantillon, cela peut créer un
signal renforcé par la pointe [33]. Le chemin optique de transmission conduit au signal
collecté de la sonde à la fibre puis au détecteur, et la lumière incidente est focalisée par la
lentille d'objectif. Les détecteurs sont des spectromètres ou des compteurs de photons
uniques (APD : Avalanche Photon Diode), donc le spectre et la photoluminescence à
résolution temporelle sont tout possible sur de tester. Il peut avoir un filtre avant que le
signal ne soit collecté sur le détecteur afin que nous puissions mesurer le signal de
fluorescence de l'échantillon. Pour le chemin optique de transmission, lorsque la sonde
polymère scanne l'échantillon, son extrémité fonctionnera également comme une micro-
lentille.
11
Chemin optique de transmission
Prism
Chemin optique de réflexion
Fig. 11 Schéma du système de microscopie optique à balayage. Le détecteur peut être

soit une photodiode à avalanche (APD), soit un spectromètre.
Le chemin optique de réflexion est un système confocal. Le faisceau laser incident illumine
l'échantillon par le bas, à travers un objectif à huile 100x, avec 1,4 N.A. Le faisceau laser
d'indentation est dévié par un miroir semi-transparent, tandis que la lumière réfléchie peut
se propager à travers ce miroir pour l'observation. Ensuite, la lumière réfléchie se sépare
en deux chemins optiques par un séparateur de faisceau 50/50, l'un vers la caméra,
surveillant l'état de l'échantillon en temps réel, et l'autre vers une lentille de focalisation afin
que le signal est couplé dans une fibre pour la détection. Le de la fibre agit comme
un trou d'épingle et le faisceau laser est focalisé pour irradier l'échantillon. Lorsque
l'échantillon est scanné, nous pouvons avoir une image d'échantillon point à point à partir
de la lumière de réflexion. Ainsi, avant que la sonde n'atterrisse sur la surface de
l'échantillon, le chemin optique de réflexion est utilisé pour caractériser la nanostructure
sur l'échantillon, en tant que la configuration de microscopie confocale (illustrée à la Fig.11).
Des filtres peuvent être insérés dans les chemins optiques, pour éliminer la lumière
d'excitation pour la mesure du signal de fluorescence.
Pour réaliser une sonde SNOM active, il est important de s'assurer que seulement
quelques émetteurs sont intégrés à l'extrémité de la sonde polymère, ainsi lors du
balayage, nous aurons une très petite source optique locale interagissant avec les
nanostructures de l'échantillon. La méthode consiste à fonctionnaliser toute la surface de
la sonde polymère, en recouvrant le groupe d'adhésion à la surface de la sonde. La
fonctionnalisation est basée sur le greffage chimique de molécules d'amine sur des
12
monomères acryliques par réaction d'addition Aza-Michael [34,35]. Il s'agit d'une réaction
d'addition conjuguée de nucléophiles donneurs d'azote à des oléfines déficientes en
électrons. Après fonctionnalisation, la surface du polymère est chargée positivement en
raison de la présence d'un groupe amine, par conséquent, les nanoparticules chargées
négativement peuvent être assemblées par interaction électrostatique [36].
Dans notre expérience, le plan approcher la sonde polymère à l'émetteur unique sur
substrat de verre, lorsque la sonde polymère touche l'émetteur, elle sera attachée à
l'extrémité de la sonde. L'avantage de cette méthode est que nous pouvons caractériser
et sélectionner l'émetteur à avance, et attacher l'émetteur exact à la sonde polymère.
Fig. 12 Absorption (ligne pointillée) et spectre d'émission des nanosphères de

fluorescence. La ligne verte indique la longueur d'onde d'excitation laser (530 nm) et
l'ombre rectangulaire orange est la plage avec filtre pour la détection
Tout d'abord, nous préparerons un échantillon avec des émetteurs séparés sur le substrat
de verre. Ici, nous choisissons des nanosphères de polystyrène à fluorescence
commerciales (FluoSpheres F8801; Invitrogen) comme émetteurs. Ce sont des sphères
de polystyrène enveloppant des molécules de colorant qui ont un pic d'absorption à 580
nm et un pic d'émission à 605 nm (voir Fig.12). Le diamètre des nanosphères est de 50
nm. Les nanosphères doivent être bien séparées, de sorte qu'il soit possible d er
une (ou quelques) nanosphères à partir du substrat de verre.
a b
Fig. 13 Caractérisation de nanosphères de fluorescence 50 nm sur un substrat de verre :

a) Image obtenue par Microscopie Electronique à Balayage (MEB) ; b) Image obtenue par
microscopie à force atomique (AFM).
En utilisant l'imagerie MEB et AFM (Fig.13), nous pouvons ajuster la concentration de
13
nanosphères dans la solution colloïdale et enfin obtenir un échantillon idéal pour la
procédure d . Ensuite, avec le confocale système de notre SNOM, nous
pouvons obtenir l'image de fluorescence de l'échantillon (Fig.14.a). Cette image de
fluorescence provient de la système confocale -à-dire, le chamin
optiaue de réflexion sur la Fig.11 (sans sonde impliquée). L'échantillon est excité par un
laser à 530 nm et filtré par un filtre passe-haut à 570 nm. Cette image de fluorescence
confirme la présence de nanosphères fluorescentes sur le substrat de verre.
Fig. 14 Balayage de l'image de fluorescence et de topographie d'une nanosphère sur un

substrat de verre : a) image de fluorescence d'une surface de 5 x 5 µm2 sur un substrat de
verre de nanosphères séparées ; b) image topographique d'une nanosphère unique
(nanosphère dans un carré rouge sur l'image précédente) obtenue par microscopie à force
de cisaillement à l'aide de la sonde polymère; c) image de fluorescence de la nanosphère
à partir d'un chemin optique de transmission, en utilisant la sonde polymère; d) image de
fluorescence de la nanosphère à partir du chemin optique de réflexion (même mode que
pour la figure a)
Nous choisissons une nanosphère isolée pour l er sur l'extrémité de la sonde

polymère. Cette nanosphère est mise en évidence par le carré rouge sur la Fig.14.a Pour
l , nous devons aligner la sonde polymère sur la position de la nanosphère.
Du coup, avant la fonctionnalisation, la sonde polymère atterrisse sur la surface de
l'échantillon, de sorte que la nanosphère unique puisse être caractérisée avec la sonde
elle-même et alignée avec la position de la sonde. Un autre faisceau laser est couplé dans
14
la fibre pour la sonde, la lumière se propageant à travers la fibre et focalisée sur l'extrémité
de la sonde. Nous pouvons observer le point focalisé de l'extrémité de la sonde. Parce que
le faisceau laser au bas est fixe, nous pouvons déplacer la sonde et laisser le point de la
sonde se chevaucher avec le point laser d'éclairage le bas. En raison de la réciprocité,
maintenant la lumière d'éclairage au bas peut être couplée via la sonde à la fibre, le signal
est détecté à partir de l'autre extrémité de la fibre en tant que chemin optique de
transmission, et dans cette situation, le chemin optique de réflexion et le chemin optique
de transmission observent la même zone. Maintenant, si nous scannons l'échantillon, nous
obtenons simultanément l'image de topographie (Fig.14.b), l'image de fluorescence de
transmission (Fig.14.c) et l'image de fluorescence de réflexion (Fig.14.d) de la nanosphère
unique, ces images portent les informations de la nanosphère et aussi indiquent la position
relative sonde-nanosphère.
Ensuite, la sonde polymère serait fonctionnalisée, de sorte qu'elle puisse avoir la capacité
de s'assembler avec la nanosphère. La sonde est retirée de l'estrade de balayage et
immergée dans la formulation pour la fonctionnalisation pendant environ 30 minutes. Après
la fonctionnalisation, nous réinstallons la sonde à l'estrade de balayage et approchons la
sonde polymère fonctionnalisée de la surface de l'échantillon. Parce que l'échantillon n'a
pas été déplacé, nous pouvons donc attacher la nanosphère pré-identifiée. Nous utilisons
le chemin optique de transmission pour aligner la position de la sonde. Quand la sonde
s'approche de la surface de l'échantillon, le laser au bas éclairant à travers la surface de
l'échantillon est collecté par la sonde. Avant que la sonde ne touche la surface de
l'échantillon, parce que la position du laser au bas est fixe, nous pouvons balayer la sonde
pour connaître la position relative entre la sonde et le point laser, puis aligner la sonde sur
la position du point laser.
Cependant, lorsque nous retirons la sonde, pour protéger la sonde, nous rétractons la
sonde à environ 1000 µm de la surface de l'échantillon, est difficile de maintenir cet
alignement lors de l'approche. Pour résoudre ce problème, nous alignons la sonde pour
chaque pas d'approche de 100 µm. De plus, avant l'atterrissage, l'échantillon est retiré de
la position de la nanosphère, afin que nous puissions atterrir la sonde sur une zone vide
du substrat de verre. Après l'atterrissage de la sonde sur la surface de l'échantillon, encore
une fois, nous déplaçons la sonde, ajustons le point optique focalisé de la sonde
chevauchant le point laser d'éclairage au bas. Une fois la sonde bien alignée, nous
ramenons la nanosphère à la position de la sonde et aussi la zone du point laser
d'éclairage au bas. Ensuite, la sonde est maintenue en contact avec la nanosphère
pendant 30 min, pour s'assurer que l'adhésion entre la sonde et la nanosphère est
terminée.
15
Fig. 15 Spectre de fluorescence de nanosphère attachée sur une sonde polymère.
a b
Fig. 16 Fluorescence d'une nanosphère unique sur le substrat de verre, a) avant

attachment ; b) après attachment (même zone), le balayage est arrêté lorsque l'ancienne
zone de fluorescence est vérifiée.
Ensuite, nous vérifions le résultat de l sur la sonde. La figure 15 montre le

spectre de fluorescence d'une nanosphère attachée sur une sonde polymère, qui a un pic
à 603 nm, en accord avec le spectre des nanosphères dans l'espace libre. Pour éviter le
photo-bleaching des nanosphères dû à une forte énergie d'excitation, nous n'utilisons
qu'une faible énergie pour exciter l'émetteur, par conséquent, le signal de fluorescence est
16
très faible. Nous rétractons la sonde de la surface de l'échantillon, si la nanosphère est
fixée avec succès à la sonde, la nanosphère quittera le substrat de verre avec la sonde.
Par conséquent, le signal de fluorescence ne peut plus être observé par le chemin optique
de réflexion (Fig.16.b).
Fig. 17 Intensité de fluorescence lorsque la sonde avec nanosphère est placée à une
distance différente de la surface de l'échantillon où le faisceau d'excitation incident est
focalisé, partie 1 ( 20 s de 40 s): 1 µm de la surface de l'échantillon (boucle de rétroaction
ouverte) ; partie 2 ( 40 s de 70 s): atterrissage sur la surface de l'échantillon.
De plus, nous rétractons la sonde à une petite distance vers un

(par exemple, si nous ouvrons la boucle de rétroaction, la sonde se rétractera d'environ 1
µm), nous observons un changement d'intensité de la fluorescence, comme le montre la
Fig.17. À la Fig.17, de 0 s à 20 s, aucune lumière d'excitation n'éclaire l'échantillon ; de 20
s à 40 s, la sonde active est à 1 µm de la surface de l'échantillon, il y a un signal de
fluorescence faible ; de 40 s à 70 s, la sonde active atterrit sur la surface de l'échantillon,
le signal de fluorescence est 2 fois plus grand que le cas précédent ; après 70 s, la sonde
active est retirée de le point laser d'éclairage, donc il n'y a pas de signal de fluorescence.
Nous caractérisons cette sonde active (avec nanosphère attachée) par MEB. Cependant,
cette caractérisation est sensible. En effet, nous avons remarqué que l'imagerie de MEB
peut tuer l'émetteur de fluorescence lors de la mesure. D'autre part, la longueur de fibre
pour une sonde SNOM est de 1 m. Pour une mesure de MEB, nous devons couper
17
l'extrémité de la fibre avec la sonde polymère. La Fig.18 est une image MEB pour sonde
active. A partir de cette image, nous remarquons que la nanosphère n'est pas attaché au
centre de la sonde, en raison de la difficulté d'alignement. La résolution optique du notre
système de champ lointain est limitée par la limite de diffraction, et lorsque nous utilisons
un laser de 530 nm pour éclairage, la résolution du système est d'environ 230 nm. Par
conséquent, , lorsque nous alignons la sonde sur le point laser
d'éclairage, l'erreur est également limitée par la résolution du système. Sur la Fig.18.b,
nous pouvons trouver que la nanosphère est située à environ 200 nm du centre de
l'extrémité de la sonde. , quand la sonde atterrit sur la surface de l'échantillon, la
sonde peut avoir un petit angle d'inclinaison, pas parfaitement perpendiculaire à la surface
d échantillon, de sorte que ce n'est pas le centre de l'extrémité de la sonde qui touche
la surface de l'échantillon, mais la zone à proximité attache la nanosphère. Étant donné
que la nanosphère a une enveloppe de polymère souple, elle est pressée de la sphère au
disque après l (illustrée à la Fig.18.b).
a b
Fig. 18 Image MEB d'une sonde polymère attachée la nanosphère, a) grossissement 40 k ;

b) Grossissement 100k
3.2 Plasmon-émetteur hybride en intégrant des nano-émetteurs au
voisinage de la nanostructure plasmonique
Dans cette section, nous rapportons des expériences de photopolymérisation sur des
nanostructures plasmon d'or. Les sites de polarisation sont contrôlés par le champ proche
plasmon local : ce sont les seuls sites où le champ optique renforcé par les plasmons peut
déclencher le processus de photopolymérisation. En utilisant des polymères
fonctionnalisés ou des formulations contenant du QD, nous pouvons placer les émetteurs
sur des parties polymérisées. Avec cette méthode, nous allons essayer d'intégrer des
nano-émetteurs au voisinage de nanocubes d'or, afin de fabriquer une hybride plasmon
nanostructure fluorescente.
18
a b
Fig. 19 Caractérisation d'un nanocube d'or unique : a) Image MEB ; b) Image AFM.
Fig. 20 Spectre de diffusion d'un seul nanocube d'or dans l'air, sur le substrat de verre.
Le nanocube d'or utilisé dans l'expérience est synthétisé par notre collègue du CEA Saclay
[37]. Ces nanoparticules sont en solution aqueuse et doivent être déposées séparément
sur un substrat de verre ITO pour le test suivant. Le verre ITO convient à l'observation
de MEB. La longueur des bords des nanocubes est de 130 nm, comme le montrent les
images MEB et AFM (Fig.19). On peut également remarquer que le nanocube a des bords
et des coins arrondis d'environ 3 nm de rayon de courbure.
En mesurant le spectre de diffusion d'un nanocube, nous savons qu'il a un pic principal à
environ 670 nm (Fig.20). Ce pic correspond à la résonance plasmon de surface localisée
dipolaire (LSPR) du nanocube [38,39]. Ce LSPR subit un décalage vers le rouge de 100
19
nm lorsque le nanocube est à l'intérieur de la formulation de polymérisation pendant la
photopolymérisation, c'est-à-dire jusqu'à 770 nm. LSPR indique une longueur d'onde avec
laquelle la lumière aura une plus forte renforcement à la surface du nanocube. Ce
renforcement local conduit à un confinement énergétique important au voisinage du
nanocube, ce qui nous aider à fabriquer une très petite structure polymère à la surface du
nanocube.
Pour correspondre à ce LSPR, nous avons utilisé la polymérisation à deux photons (TPP)
dans l'expérience. Comparé à la polymérisation à un photon (OPP) que nous avons utilisée
pour fabriquer la sonde polymère, le TPP est un processus non linéaire qui est excité par
l'absorption de la lumière à deux photons [40]. Lors d'une exposition dans le proche
infrarouge, l'initiateur de photons peut être activé en absorbant deux photons
simultanément. Pour un seul événement quantique, l'énergie correspond au spectre de la
région UV, qui correspond l'initiateur (IRG819) utilisé dans cette
expérience. Le taux de polymérisation du TPP est proportionnel au carré de l'intensité des
photons, ce qui conduit à une précision spatiale 3D beaucoup plus élevée que pour l'OPP
pour placer la nanostructure polymère très près du nanocube d'or.
Fig. 21 Images MEB des structures hybrides sur nanocube d'or résultant de TPP
plasmonique, avec exposition de polarisation incidente le long de la direction x : a) bord
20
du côté du cube parallèle à la polarisation de la lumière incidente ; b) Calcul FDTD de
l'intensité plasmonique en champ proche utilisé pour le TPP plasmonique résultant en a);
c) diagonale parallèle à la polarisation de la lumière incidente ; d) Calcul FDTD de
l'intensité plasmonique plasmonique en champ proche utilisé pour le TPP plasmonique
résultant en c).
Pour la photopolymérisation, un laser Ti:Sapphire femtoseconde de 780 nm a été utilisé

pour l'exposition. Le laser incident est focalisé par une lentille d'objectif (N.A. = 0,6), et le
nanocube unique est observé par un éclairage en lumière blanche sur fond noir, de sorte
que nous pouvons facilement localiser le nanocube à la position du point laser. En raison
du renforcement d'énergie locale à la surface du nanocube, nous utilisons une dose
d'exposition plus faible que le seuil de polymérisation. La dose seuil (D th) est mesurée
préalablement au niveau de la zone vide de l'échantillon. L'énergie du champ proche
diminue très rapidement en s'éloignant de la surface du nanocube. En utilisant différentes
doses d'exposition, nous pouvons intégrer différents volumes de polymère polymérisé à la
surface du nanocube. En général, les nanoparticules photopolymérisées obtenues
reproduisent la distribution d'énergie en champ proche. La figure 21 montre des
nanostructures hybrides résultantes avec deux orientations de cube par rapport à la
polarisation incidente. De cette façon, différents nanovolumes de polymère sur nanocube
peuvent être obtenus, grâce au contrôle de la distribution d'énergie plasmon en champ
proche.
Après le polymère est fonctionnalisé avec un groupe d'adhésion, la nanosphère

fluorescente peut être attachée, comme ce que nous avons fait pour la sonde active. En
immergeant les nanostructures hybrides dans une solution de nanosphère, la nanosphère
peut attacher à la surface du polymère fonctionnalisé. Avec différentes épaisseurs de
polymère, nous pouvons contrôler la distance entre les émetteurs et le nanocube [39]. Sur
la Fig.22, nous voyons qu'avec une dose d'exposition plus élevée, l'épaisseur du polymère
à la surface du nanocube est plus loin, ce qui entraîne de nombreuses nanosphères
attachées (Fig.22.a). Pour une épaisseur plus faible, seules quelques nanosphères
attachons à la nanocune (Fig.22 .b).
21
(c)
Fig. 22 Nanosphères attachées à la surface du nanocube avec différentes épaisseurs de

polymère correspondant à différentes doses d'exposition de photopolymérisation : a) 40 %
Dth ; b) 10 % Dth. c) Image MEB de différentes tailles de polymère sur nanocube par
différentes doses d'exposition de 80 % à 10 %.
Une fois les nanosphères attachées au voisinage du nanocube, elles pourraient être
sélectivement excitées par les plasmons de surface locaux du nanocube. En modifiant la
dose d'exposition, nous pouvons obtenir différentes épaisseurs de polymère. Cette
épaisseur sert d'espaceur entre le nanocube et les nanoémetteurs. Nous avons analysé
la décroissance de la durée de vie des émissions de ces différents systèmes hybrides. À
partir de la Fig.23, nous pouvons voir que la durée de vie de la nanosphère diminue lorsque
la dose d'exposition diminue. Lorsque la dose d'exposition diminue, les nanosphères
attachées se rapprochent de plus en plus du nanocube, ce qui entraîne une durée de vie
plus courte. La durée de vie en espace libre de la nanosphère est ajustée par une fonction
exponentielle d'environ 6,3 ns. Et la décroissance la plus rapide sur la Fig.23 est l'IRF
(fonction de réponse de l'instrument), qui est d'environ 0,6 ns, indiquant la résolution du
système expérimental. La durée de vie des nanosphères passe de 6,3 ns (en espace libre)
à moins de 1 ns. En général, une tendance intéressante est démontrée : l'épaisseur du
22
polymère à la surface du nanocube joue un rôle d'espaceur, ce qui se traduit par une
distance réglable entre le nanocube et la nanosphère. C'est pourquoi on constate une
diminution de la durée de vie lorsque la dose d'exposition diminue.
Fig. 23 Décroissance différente de la durée de vie des nanosphères lorsque la nanosphère

a été attachée sur un système cube-polymère avec une dose d'exposition différente.
Pour émetteurs plasmons hybrides basés sur la photopolymérisation, nous avons

également utilisé des semi-conducteurs Quantum Dots (QDs, émission à 620 nm, excités
par un laser à 405 nm) au lieu de nanosphères de fluorescence. Dans ce cas, les QDs
sont distribués de manière aléatoire à l'intérieur de la formulation polymérisable afin de les
piéger localement par photopolymérisation. Les QDs sont situés presque sur tout le
nanovolume de polymère. Par exemple, comme le montre la Fig.21.c, si nous effectuons
une photopolymérisation avec la polarisation de la lumière incidente parallèle à l'axe
diagonal du cube, nous obtenons deux lobes de polymère aux coins du cube. Étant donné
que les QD sont mélangés dans la formulation de polymère, ils émettent de la lumière à
partir de ces deux lobes lorsqu'ils sont excités. En d'autres termes, les QDs sont tous
situés aux points chauds du plasmon en champ proche du nanocube. Profitant de cette
position sélective au voisinage du cube et de l'anisotropie du milieu actif qui en résulte, on
pourrait exciter sélectivement les QDs en contrôlant la polarisation de la lumière incidente.
Considérant cette hybride système d'émission de plasmon, qui a deux lobes polymères
contenant des QDs sur les coins diagonaux, lorsque l'orientation de polarisation de la
lumière d'excitation incidente est parallèle à la diagonale a des QDs, le signal de
fluorescence est observé à partir de ce système. D'autre part, pour une polarisation
23
incidente perpendiculaire à la diagonale a des QDs, du fait que le point chaud d'énergie
se trouve au coin sans QDs, le signal de fluorescence est faible. En conséquence, nous
avons trouvé deux états d'émission clairement différents pour ces deux orientations de
polarisations différentes.
De plus, le plasmon-émetteur hybride commutable peux être étendu au régime de photon

unique [13]. En diminuant la concentration de QD dans la formulation de
photopolymérisation, nous obtenons une structure hybride qui n'a qu'un ou quelques QD
à l'intérieur des lobes de polymère sur le coin de cube. La figure 24.a montre une image
AFM d'un tel plasmon-émetteur hybride. Le nanocube d'origine est parallèle en diagonale
à l'axe X, conduisant à des lobes de polymère le long de l'axe X après polymérisation à
avec une lumière d'exposition polarisée horizontale. Un laser pulsé de 405 nm avec une
polarisation horizontale est utilisé pour exciter la fluorescence. Avec une système Hanbury
Brown-Twiss [41] couplé à un système de balayage confocal sensible à l'émission d'un
émetteur quantique unique, nous pouvons voir un clignotement clair de la Fig.24.b et de la
Fig.24.c, qui est la signature d'une seule (ou de quelques) émission de QDs. Sur la
Fig.24.b, cette émission est désactivée lorsque la polarisation incidente est tournée vers
la polarisation verticale en raison du manque soudain de chevauchement entre le champ
proche d'excitation et le QD. Nous avons constaté qu'à un retard nul, la fonction
d'autocorrélation [42] g(2)(0) 0,35 (Fig.24.d), qui est inférieur à 0,5, illustrant qu'il n'y a
qu'un seul photon émis en même temps. Nous utilisons un laser pulsé à fréquence de
répétition de 5 MHz pour l'IRF et la mesure de la durée de vie et avons obtenu un IRF
d'environ 0,63 ns. Plusieurs nano-émetteurs hybrides typiques sont mesurés, leur
décroissance de durée de vie est présentée sur la Fig.24.e. La durée de vie typique d'un
plasmon-émetteur hybride est de 0,725 ns, tandis que la durée de vie des QDs en
polymère a été mesurée à environ 17,5 ns (Fig.24.f). Ces mesures correspondent à un
facteur Purcell moyen de 17,5/0,725 23. Ici, la mesure de la durée de vie des QDs
piégés dans la nanostructure hybride est limitée par la résolution temporelle de notre
système TCSPC.
24
Fig. 24 Plasmon-émetteur hybride en régime de photon unique. a) Image AFM de
plasmon-émetteur hybride à base de nanocubes, un ou quelques QD contenus dans les
lobes de polymère ; b), c) trace de spectre fluorescent avec lumière incidente de
polarisation linéaire horizontale à 405 nm. En b) à 32 s, la direction de polarisation est
tournée vers la verticale. d) mesure de g(2) montrant g(2)(0) = 0,35. e) décroissance de
durée de vie de trois de plasmons-émetteurs hybrides différents contenant un ou peu de
QD. f) comparaison de durée de vie entre QD dans le polymère et QD au voisinage du
25
nanocube d'or.
4 Étude des nanostructures avec la nouvelle sonde polymère
4.1 Balayage sur la surface de nanofil d'argent avec une sonde polymère
Dans cette section, nous essayons d'étudier l'interaction lumière-matière au niveau des
nanofils d'argent (silver nanowire, Ag-NW), en détectant le champ proche optique capté
par la sonde polymère balayant le nanofil. Les nanofils métalliques peux supporter des
polariton plasmonique de surface (SPP) qui est lancés et détectés aux extrémités avec
une lentille d'objectif à grande ouverture numérique [43][44]. Lorsque la sonde polymère
balaye sur Ag-NW, parce que le rayon de l'extrémité de la sonde est proche du diamètre
du NW et que la distance de balayage de travail est inférieure à 20 nm, le champ
évanescent de SPP pourrait se coupler à la sonde, puis ce signal de champ proche
passera par la fibre optique et pourra être détecté [46].
Les Ag-NW (Sigma-Aldrich, réf. 739448) sont dilués dans une solution d'isopropanol. Ces
NW ont une longueur de 5 à 50 µm et un diamètre de 115 nm. À partir de l'image MEB
(Fig.25), nous pouvons voir la surface lisse sans défaut et l'extrémité à facettes de NW,
telle qu'elle est développée chimiquement, ce qui donne une structure monocristalline.
Fig. 25 Image MEB d'un nanofil d'argent
nous balayons d'abord l'échantillon pour trouver la position des NW par le système
confocal, pour sélectionner un bon NW pour l'expérience. Parce que la longueur de SPP
26
d'un NW est toujours inférieure à 10 µm [46][47], nous devons choisir un NW court et droit,
afin que nous puissions facilement surveiller le SPP à partir de la diffusion de l'extrémité
NW [45][48]. En plaçant l'extrémité de NW au point de focalisation du laser par une lentille
d'objectif à grande ouverture numérique et en ajustant la direction de polarisation, le
lancement de SPP est clairement observé en diffusant l'autre extrémité de l'extrémité NW
[43][49]. La configuration est illustrée à la Fig.26.
Fig. 26 Excitation des plasmons de surface par un objectif à grande ouverture numérique
de l'extrémité de NW [49].
Une fois le SPP excité, la sonde polymère intégrée sur fibre optique est approchée de
l'échantillon. Après l'atterrissage, la sonde balaye le NW, pour collecter la topographie et
le signal optique de champ proche de la surface du NW. Ici l'échantillon ne bouge pas,
pour maintenir l'excitation de SP sur le nanofil, et la sonde scanne sur le nanofil. Le signal
est collecté par le chemin optique de transmission (voir Fig.11). La figure 27 montre une
analyse de résultat en champ proche.
a b c
Fig. 27 Image de balayage du SP sur nanofil, a) image de topographie du nanofil ; b) un

signal optique en champ proche collecté à partir de la surface du nanofil par la sonde
polymère ; c) courbe du profil d'intensité au centre de l'image optique, le long de la ligne
rouge indiquée en b).
27
Dans l'image topographique (Fig.27.a), nous pouvons voir que la longueur de ce NW est
chemin optique de transmission du système
SNOM, montrant le signal SP en champ proche sur la surface de l'échantillon (Fig.27.b).
L'intensité SP s'amortit de manière exponentielle pendant la propagation le long du nanofil,

décrite comme l'équation suivante,
(Eq.1)
Lspp est la longueur de propagation du plasmon de surface, d est la distance de

propagation. A partir de cette équation, on ajuste la courbe d'intensité avec une fonction
exponentielle, on trouve Lsp = 475 nm (voir Fig.28). Cependant, la longueur de propagation
SP typique pour le nanofil d'argent pour la lumière verte est supérieure à 1 µm. Dans notre
cas, la raison est une couche de soufre d'environ plusieurs nanomètres recouvrant le
nanofil d'argent à cause de la sulfuration (Fig.29).
Fig. 28 Ajustement exponentiel pour la courbe d'intensité le long de la surface du nanofil
28
Glass Silver
a b
Silver Sulfide
Ag
Glass
Fig. 29 a) Géométrie de simulation de fil d'argent sur substrat de verre. b) Vue latérale de
la géométrie, le fil d'argent est recouvert d'une couche de sulfure d'argent et placé sur un
substrat de verre.
Dans cette mesure, parce que la sonde polymère peut collecter à la fois le champ
évanescent et le signal de champ lointain, nous avons en fait observé la superposition de
l'onde SP et de l'onde d'excitation diffusée. Par conséquent, pour une imagerie claire en
champ proche, il est important d'éliminer le signal de fond lors de la détection. C'est
pourquoi le nanoémetteur en tant que source de lumière locale est nécessaire pour la
sonde active, car la lumière d'excitation de fond peut être supprimée par filtrage spectral.
4.2 Balayage de nanocube d'or en utilisant une sonde active
Dans cette section, nous étudierons les nanocubes d'or en utilisant une sonde active. Des
nanocubes (taille de 130 nm) est étudiés en déposant une faible concentration de solution
colloïdale de nanocubes sur un substrat de verre. L'interaction lumière-matière entre
l'émetteur et le nanocube est détectée par le chemin optique de réflexion de la lumière à
travers l'objectif et le chemin optique de transmission à travers la sonde. La sonde
polymère a un rayon de 200 nm, et avec une nanosphère de fluorescence de 50 nm à son
extrémité. Le processus de fabrication de cette sonde active a été présenté au chapitre 3.
Une mesure de photoluminescence résolue temporelle est effectuée pendant le balayage
pour discuter de l'évolution de la durée de vie de la fluorescence avec la présence du cube.
Après l'atterrissage de la sonde active sur la surface de l'échantillon, nous devons déplacer
la sonde vers le point laser d'éclairage au bas, afin d'aligner le chemin optique de réflexion
et de transmission (voir Fig.11). À partir du chemin optique de transmission, un laser de
530 nm est couplé dans la fibre, puis se propage jusqu'à l'extrémité de la sonde. Lorsque
nous balayons la sonde sur une zone vide du substrat en verre, à partir du chemin optique
de réflexion, nous pouvons observer que la lumière se propage à travers la sonde et le
point indique la position de la sonde (Fig.30.a). Si nous ajoutons un filtre avant le détecteur
et balayons la sonde dans la même zone que l'image précédente, nous pouvons obtenir
une image de point de fluorescence de la sonde à = 603 nm (Fig.30.b). Cette émission
de fluorescence provient de la nanosphère attachée à la sonde et nous pouvons constater
29
que le point de fluorescence n'est pas à la même position que le point à 530 nm de
l'extrémité de la sonde sur l'image précédente. Il y a un décalage spatial d'environ 200 nm
entre le point à 530 nm du centre de l'extrémité de la sonde et le point de fluorescence à
603 nm de la nanosphère.
a b
Fig. 30 a) Illumination de la sonde à la surface de l'échantillon à = 530 nm. b) image de

fluorescence à =603 nm de la sonde, due à la nanosphère de fluorescence sur la sonde
(même illumination que pour image a).
Pour une émission de fluorescence stable, nous préférons aligner la nanosphère sur la
position du point laser d'éclairage au bas plutôt que sur le centre de l'extrémité de la sonde.
Considérant le balayage de l'échantillon avec laser d'éclairage au bas, la figure 31 illustre
la taille et la position relatives de la sonde polymère, de la nanosphère et du nanocube. La
surface de la sonde polymère a été approximée par une parabole, avec une courbure de
200 nm en bas. La nanosphère se localise donc à la surface de la sonde polymère à 200
nm du centre.
30
Illumination
laser
Fig. 31 Schéma de sonde polymère avec nanosphère et nanocube (unité : µm)
Nous avons d'abord enregistré l'image de fluorescence et l'image de topographie

simultanément en balayant l'échantillon (Fig.32). Comme décrit ci-dessus, la nanosphère
sur la sonde est alignée sur le point laser d'illumination au bas. Ce laser incident à 530 nm
excite la nanosphère sur sonde, la nanosphère active devient alors une source lumineuse
de fluorescence locale à 603 nm. Pendant le balayage de l'échantillon, lorsque le
nanocube interagit avec la sonde active, la fluorescence de diffusion est collectée
simultanément à partir de la lentille d'objectif au bas ("chemin optique de réflexion", illustré
en 32.a) et à travers la fibre optique de la sonde polymère ("chemin optique de
transmission", illustré en 32.c), en utilisant un filtre passe-haut respectivement sur les deux
chemins optiques. Nous obtenons également l'image de la topographie de ce nanocube
en même temps (Fig.32.d).
Le schéma de configuration de la sonde (Fig.31 et Fig.35) peut nous aider à comprendre

les images obtenues. Parce que nous utilisons un mode de hauteur constante pour le
balayage, l'image topographique est une convolution de la surface de la sonde polymère
active et du nanocube. De la Fig.34, nous pouvons voir un épaulement sur la partie droite,
qui correspond à l'emplacement de la nanosphère illustré sur la Fig.31. De la Fig.32.a, on
peut voir une ombre faible correspondant à l'image topographique du nanocube, une
ombre sombre au centre et un petit point lumineuse proche de l'ombre sombre, qui
31
correspond à la position de la nanosphère (Fig.33, Fig.34) . La Fig.32.b est une image
agrandie pour le point le plus brillant de la Fig.32.a, en réduisant la zone de balayage à
200 nm x 200 nm carré.
a b
c d
Fig. 32 Image de balayage (avec sonde active atterrit sur la surface de

) du nanocube d'or : a) image de fluorescence à partir du chemin optique de
réflexion ; b) zoom de la partie lumineuse de l'image a) ; c) image de fluorescence du
chemin optique de transmission ; d) image topographique du cube, signal simultané avec
le signal de réflexion et de transmission.
Fig. 33 Profil selon la ligne rouge de l'image topographique du nanocube sondé par la
sonde polymère (Fig.5.32.d)
32
Fig. 34 Profil le long de la ligne rouge de l'image de réflexion de fluorescence avec la sonde
active au-dessus du nanocube (Fig.5.32.a)
Parce que la nanosphère est alignée sur la position du point laser d'excitation incident
(Fig.31), la nanosphère est toujours activée avant que la sonde ne rencontre le nanocube
pendant le balayage, ce qui conduit à un fond lumineux sur la Fig.32.a. Lorsque le
nanocube s'approche de la sonde (Fig.35.b), un bord du nanocube entrera d'abord en
contact avec la surface de la sonde, et la sonde se soulèvera avec le profil de la surface
de la sonde, ainsi la nanosphère se soulèvera également du point focal d'excitation point
laser, et l'intensité de la fluorescence diminuera avec la distance entre la nanosphère et le
point focal, ce qui entraînera une faible ombre sur l'image. Lorsque la sonde balaye vers
le haut du nanocube, parce que c'est la position la plus élevée du cube, la nanosphère est
également à la position la plus éloignée du point focal, elle émet donc la plus faible intensité
de fluorescence. Dans la région du champ proche, le champ local n'est renforcé qu'à la
surface du nanocube le long de l'orientation de polarisation de la lumière incidente, lorsque
la nanosphère est au sommet du nanocube, le laser d'excitation du bas sera bloqué. C'est
pourquoi la zone d'ombre sombre apparaît.
Une fois que la nanosphère se déplace du haut vers le bord du nanocube, la nanosphère
s'approche du champ proche renforcé du nanocube (Fig.35.d), ainsi l'intensité de
fluorescence augmente, montrant un point lumineux proche de l'ombre sombre (Fig.34).
Grâce au renforcement du champ proche du nanocube, l'intensité de la fluorescence est
clairement amplifiée. Sur la Fig.34, nous pouvons voir au point lumineux que l'intensité de
fluorescence est de 500, tandis que l'intensité de l'espace libre est de 350. Et nous prenons
la partie la plus sombre de la courbe comme signal de fond, par conséquent, l'intensité de
fluorescence est amplifiée d'environ 1,5 fois lorsque la nanosphère touche le bord du
nanocube. Il convient de noter que la résolution de notre système confocal est de 230 nm,
alors que cette image de fluorescence à balayage a une meilleure résolution et, en d'autres
termes, dépasse la limite de diffraction. D'après la Fig.32.b, la taille du point est d'environ
40 nm, correspond à la taille des nanosphères 50 nm.
33
a
Fig. 35 Nanocube à différentes positions pendant le balayage de l'échantillon lorsque la

sonde active atterrit sur : a) la sonde atterrit sur le substrat ; b) un
bord du nanocube contacte la surface de la sonde; c) la sonde polymère au sommet du
nanocube ; d) nanosphère sur le bord du nanocube
La figure 32.c montre l'image de balayage par fluorescence signal de chemin optique de
transmission. Ce signal de transmission est collecté par la sonde et se propage à travers
la fibre jusqu'au détecteur. Malheureusement, du fait de la délocalisation de la nanosphère
par rapport au centre de la sonde, la sonde ne peut pas très bien capter le signal de
fluorescence, on ne voit qu'une très faible ombre à l'image. Il n'y a plus d'informations
intéressantes à partir de l'image de fluorescence de transmission en raison du faible signal.
La nanosphère doit être précisément alignée au centre de la sonde, si l'on veut avoir une
bonne image de fluorescence en transmission dans cette configuration.
Ces résultats ci-dessus prouvent une chose : à partir du chemin optique de réflexion, nous
pouvons obtenir une partie de la distribution en champ proche à la surface du nanocube,
cette image en champ proche provient en fait du signal de fluorescence excité par le champ
local. Etant donné qu'un seul bord du nanocube peut entrer en contact avec la nanosphère,
seul le champ local de ce bord peut être observé. Il a été souligné que le champ local du
nanocube est très sensible à la direction de polarisation de la lumière incidente, nous
pouvons étudier le changement de champ local sur le bord du nanocube lorsque la
direction de polarisation de la lumière incidente change. La Fig.36 montre le résultat de
l'expérience, l'image fluorescente par chemin optique de réflexion pour le cube. Pour
observer facilement, la luminosité et le contraste de ces images sont modifiés. Lorsque la
direction de polarisation passe de la verticale à l'horizontale, le point lumineux proche de
34
l'ombre sombre se déplace de la moitié inférieure du bord (Fig.36.a) vers la moitié
supérieure (Fig.36.b).
a b
E E
Fig. 36 Image de fluorescence à partir du chemin optique réflexion, avec une direction de
polarisation différente de la lumière d'excitation incidente : a) polarisation verticale ; b)
polarisation horizontale.
Cela est dû au fait que le champ local renforcé sur ce bord passe de la moitié inférieure à
la moitié supérieure lorsque la direction de polarisation change. La figure 37 montre le
calcul FDTD du champ proche local au voisinage du nanocube avec une direction de
polarisation différente de la lumière d'excitation incidente (530 nm). Selon l'ombre sombre
de la Fig.36
d'une montre à partir d'un carré standard. Pour la Fig.37.a, lorsque la polarisation de la
lumière incidente est verticale, sur le bord droit, le point chaud se situe dans la moitié
inférieure, tandis que pour la Fig.37.b, lorsque la polarisation est horizontale, le point chaud
se situe dans la moitié supérieure. Et cette simulation explique le résultat de l'expérience
à la Fig.36. Par conséquent, une fois que la nanosphère de fluorescence entre en contact
avec le nanocube, l'image de fluorescence peut représenter le champ proche au voisinage
du nanocube, dans cette expérience, seul le champ proche d'un bord du cube peut être
observé. Pour une meilleure imagerie, en d'autres termes, obtenir plus d'informations de
champ proche, il est nécessaire de trouver une méthode pour que le nanoémetteur
contacte plus de parties de la nanostructure, par exemple, pour placer la nanosphère au
centre exact de l'extrémité de la sonde.
35
a b
E E
Fig. 37 Simulation FDTD du champ proche au voisinage du nanocube, par une lumière
d'excitation à 530 nm avec une direction de polarisation différente : a) polarisation verticale ;
b) polarisation horizontale
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39
Hongshi CHEN
Doctorat : Matériaux, Mécanique, Optique et Nanotechnologie
Année 2022
Sonde active pour SNOM et l'interaction Contribution to Active Probe for SNOM
lumière-matière nanométrique basée and Nanoscale Light-matter Interaction
sur la photopolymérisation based on Photopolymerization
La microscopie optique en champ proche à balayage Scanning Near-field Optical Microscope (SNOM) is a
(SNOM) est une technologie d'imagerie optique à technology for high resolution optical imaging. The
haute résolution. L'information associée aux hautes high spatial frequency information from the near-
fréquences spatiales du champ proche est associée field is associated to high spatial resolution, allo-
à une haute résolution spatiale, permettant de wing one to break the diffraction limit. The used
dépasser la limite de diffraction. Développer une local probe is still a key topical issue that has been
sonde optique locale efficace reste un sujet clé addressed for long. The thesis deals with the deve-
d'actualité qui est abordé depuis longtemps. La lopment of an active near-field probe based on a
thèse porte sur le développement d'une sonde en polymer tip integrated at the extremity of an optical
champ proche active basée sur une pointe polymère fiber. We polymerized polymer tip on the surface of
intégrée à l'extrémité d'une fibre optique. Nous the fiber end as a scanning optical probe. Shear-
avons polymérisé une pointe en polymère sur la force method with micro tuning fork is used for
surface de l'extrémité de la fibre. Pour balayage, les controlling the probe-sample distance. After surface
forces locales de cisaillement détectées à l’aide d’un functionalization of the polymer probe, a few nano-
micro diapason sur lequel est collé la sonde sont emitters have been attached on the probe extremity,
utilisées pour contrôler la distance sonde- to obtain an active probe. Upon excitation, the nano-
échantillon. Après fonctionnalisation de surface de emitters can act as local light source for the active
la sonde polymère, quelques nano-émetteurs ont été probe. Besides, while the development of such ac-
attachés sur l'extrémité de la sonde, pour obtenir tive hybrid probes turned out to be challenging, the
une sonde active. Les nano-émetteurs peuvent servir developed strategy of attachment has been used on
de source lumineuse locale pour la sonde active. La gold nanocubes on substrate, to create polarization-
stratégie d’intégration de nano-emetteurs dévelop- sensitive hybrid plasmon nano-emitters. We also
pée a été utilisée sur des nanocubes d'or sur sub- extended this hybrid nano-emitters to single photon
strat, pour concevoir des nano-émetteurs de plas- regime. Finally, the active probe was tested on two
mons hybrides sensibles à la polarisation. Nous kinds of samples: silver nanowires and gold nano-
avons également étendu ces nano-émetteurs hy- cubes. By using our new active probe, we obtained
brides au régime de photon unique. Enfin, la sonde near-field information for those nanostructures and
active a été testée sur deux types d'échantillons : broke the diffraction limit.
des nanofils d'argent et des nanocubes d'or. En
utilisant notre nouvelle sonde active, nous avons
collecté des informations de champ proche pour ces Keywords: nanotechnology – nanophotonics – near-
nanostructures et dépassé la limite de diffraction. field microscopy – photopolymerization – plasmons
(physics).
Mots clés : nanotechnologie – nanophotonique –

microscopie en champ proche – photopolymérisa-
tion – plasmons.
Thèse réalisée en partenariat entre :
Ecole Doctorale "Sciences pour l’Ingénieur"

Hongshi Chen 2022TROY0007

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Contribution to Active Probe

2022TROY0007 Année 2022

en SCIENCES POUR L’INGENIEUR

Spécialité : MATERIAUX, MECANIQUE, OPTIQUE ET NANOTECHNOLOGIE

présentée et soutenue par

Contribution to Active Probe for SNOM and Nanoscale

M. Régis BARILLÉ PROFESSEUR DES UNIVERSTES Président (Rapporteur)

Scanning Near-field Optical Microscope (SNOM) is a technology for high

Chapter 1 is a detailed introduction that presents the framework and remind

1.1 Scanning near-field optical microscopy: attempt to breaking

In traditional far-field optical imaging, the spatial resolution is limited by the

For getting a light-emitting probe, we have used nanoemitters (Quantum Dots,

According to the Bethe-Bouwkamp-Theory, emission of a small aperture is

1.1.1 SNOM principles

Fig.1. 1 Schematic of plane wave diffraction on an arbitrary object

When we consider a general problem: scattering of light by an arbitrary object,

, is the wave vector components of corresponding coordinates. Because

Which is known as angular spectrum representation. means the position

Therefore, the angular spectrum is a superposition of propagating plane waves

covered by evanescent waves. Therefore, these high special frequencies

Fig.1. 2 Imaging information from a sample plane (z = 0) to a detector plane (z = z ) using

Consider the configuration of classic SNOM illumination (Fig.1.2), a probe apex

When the field propagates to the sample plane we have:

The sample can be characterized by a transmission function .To simplify

Then the sample field will propagate to far-field detection plane at z = z ,

Obviously, the field been detected is a far-field. We define as

If we take numerical aperture NA of the collection objective lens into accout we

frequency ( ), ie near-field evanescent waves. For the convolution, we

demonstrate two specific points: 1. , the largest transverse

wavenumber for propagating plane wave; 2. , large spatial frequency

propagation wave (gray area inside thick black circle); When

We also notice that, to transfer information from near-field to far-field, higher

1.2.1 Surface plasmons

Since we choose metal nanostructures for our test sample, it is important to

is the electron effective mass, is the electron charge. is the

, whereas is the dielectric constant of high frequency limit, is the

is predominantly real, and when , metals retain their metallic

Localized surface plasmon resonance (LSPR)

When incident electromagnetic waves interact with sub-wavelength metallic

The localized surface plasmons might be influenced by nanostructure

1.2.2 Metal enhanced fluorescence

Fig.1. 5 Simplified Jablonski diagram metal enhanced fluorescence process

When emitter is placed at suitable distance from metallic nanostructures, an

1. Hecht, E., 2016. Optics. 5th ed. Pearson.

Optical Nanosources. ACS Nano, 4(2), pp.759-764.

In this chapter, we will introduce how to fabricate a micro polymer probe on

2.1 Photopolymerization reaction

Photopolymerization is a well-known and well-developed method for fabrication

There are two major components for a photopolymerization formulation: photon

is the monomer and n, m indicate the number of the monomer in the

2.1.1 Formulation composition

The monomer used for our formulation is PETA (pentaerythritol triacrylate,

Fig.2. 1 Chemical species contained in the photopolymerizable formulation a) PETA

The absorption spectrum of the formulation is shown in Fig.2.2, it shows a good

2.1.2 Polymer stiffness

By using a commercial Atomic Force Microscope from Bruker, we could

0.25 GPa, slightly smaller than the IPN

Exposure: laser beam

Fig. 2. 5 Mode field diameter of optical fiber [5]

2.2.1 FDTD simulation for photopolymerization on fiber end

Therefore, it is a continuously changing process. For calculation, a recursive

To simulate the experiment, we set the parameters as defined by the actual

Fig.2.6 shows the simulation of 10 time-iterations for 1 s total exposure time.