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 19

Optical Deposition of Carbon Nanotubes

for Fiber-based Device Fabrication
Ken Kashiwagi and Shinji Yamashita
Department of Electronic Engineering, The University of Tokyo
Japan

1. Introduction
Since carbon nanotubes (CNTs) have been applied to a passive mode-locker, or a saturable
absorber (Set et al., 2004a; Set et al., 2004b), applications of CNTs in photonics field have
been intensively investigated. Their quasi-one-dimensional structures produce their
distinctive characteristics, their strong third-order nonlinearity and ultrafast recovery time,
shorter than 1ps (Chen et al., 2002; Ichida et al., 2002). These characteristics are attractive for
future ultrafast photonic networks and can be used in ultrafast photonic devices, such as
ultrafast all-optical switches and all-optical logic gates.
Since CNTs are nano-sized material, one of the largest problems to realize CNT-based
devices is handling issue. Optical deposition method has an advantage in efficiency over the
other handling methods, such as spraying (Set et al., 2004a; Set et al., 2004b), direct synthesis
(Yamashita et al., 2004), and polymer embedding methods (Sakakibara et al., 2005). These
methods mostly require complicated processes, large-scale setups, and dissipate significant
numbers of CNTs. A simpler and more cost effective handling technique of CNTs is
required for mass productive CNT-based optical devices. We proposed optical CNT
deposition technique to solve the problem. The light injection into CNT-dispersed solution
from an optical fiber end deposited CNTs onto core region of the optical fiber end. We
realized a passively mode-locked fiber laser using the CNT-deposited fiber as a saturable
absorber, or a passive mode-locker.
However, the technique requires very precise control of the light injection power to deposit
uniform and less scattering CNT layer, because highly uniform CNT solution, which has
very small CNT entanglements, is required. Smaller CNT entanglements require higher
injection power. High power injection makes the CNT layer around the core, not on the
core. The upper limit of optical intensity depends on the flow speed caused by the injected
light. Additional technique is, accordingly, needed to optimize injection power for each
solution. We introduced in-situ optical reflectometry to monitor the deposition process, and
area-selectively deposited CNTs onto core regions of optical fiber ends. The area-selectivity
was confirmed by field emission scanning electron microscope (FE-SEM).
The technique has been applied only to deposition of CNTs onto fiber ends, though it has
potentially versatile applications. We propose and demonstrate optically induced deposition
of CNTs around microfibers by injecting light through the fibers. We also demonstrate a
passively mode-locked fiber laser using a CNT-deposited microfiber fabricated by the
technique.
Source: Frontiers in Guided Wave Optics and Optoelectronics, Book edited by: Bishnu Pal,
ISBN 978-953-7619-82-4, pp. 674, February 2010, INTECH, Croatia, downloaded from SCIYO.COM

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386 Frontiers in Guided Wave Optics and Optoelectronics

In this chapter, we report optical deposition of CNTs onto optical fibers to realize simple
and low cost fabrication of CNT-based fiber-structure devices. This chapter is organized as
follows. In section 2, we explain CNT-based optical devices, including fundamental
properties of CNTs, CNT fabirication methods, and structures of CNT-based optical devices.
We propose the technique to deposit CNTs using light injection in section 3. In section 4, we
show the technique with optical reflectometry to enhance the performance of the technique
in terms of CNT-use efficiency and repeatability. We report application of the technique to
CNT deposition around microfibers in section 5. Finally, we summarize this chapter in
section 6.

2. Optical device based on carbon nanotubes

2.1 Carbon nanotubes fabrication methods
Graphite and diamond have been well known allotropes of carbon. In 1985, the third
allotrope of carbon, fullerene, was discovered by Kroto et al. (Kroto et al., 1985), and carbon
based nanomaterial research field emerged. CNTs are the forth new group of carbon
materials which have nearly identical one-dimensional cylindrical structures, and their
structures are assumed to be rolled sp2-bonded graphene sheets. Graphene sheet is a sheet
which carbon atoms are hexagonally bonding with each other. Since the discovery of CNTs
by Iijima in 1991 (Iijima, 1991), theoretical studies of CNTs have been intensively examined.
The studies brought out the distinctive physical properties of CNTs, such as their electronic
density of states (eDOS), and metallic and semiconducting distinction that depends only on
their structure, chirality (Saito et al., 1992). There are two types of CNTs in terms of their
structures, single walled nanotubes (SWNTs) have only single cylinder, and multi walled
nanotubes (MWNTs) have two or more cylinders. The CNTs which have optically
interesting properties are the SWNTs.
Experimental studies on CNTs became possible after the establishment of production
methods in the late 1990s, such as laser-furnace (Guo et al., 1995), arc-discharge (Journet
et al., 1997), and catalytic CVD methods with supported catalysts (Dai et al., 1996) and
floated catalysts (Satishkumar et al., 1998). These methods are used in the mass synthesis of
CNTs in which the CNTs are obtained as soot adhered on the wall of the production
chambers. Since the as-synthesized soot contains amorphous carbons, multi-shelled
graphites, fullerenes, and/or catalyst metal particles as impurities, a purification process is
generally required prior to use (Bandow et al., 1998; Bai et al., 2004; Chiang et al., 2001;
Colomer et al., 1999; Morishita & Takarada, 1999; Park et al., 2006). The high pressure carbon
mono-oxide (HiPco) method (Nikolaev et al., 1999) has been one of the commercialized
fabrication methods for the mass production of CNTs.
The development of production methods of CNTs enabled experimental studies for specific
applications. One of the applications is saturable absorbers for ultrashort pulse generation.

2.2 Optical characteristics of carbon nanotubes

In the previous subsection, we reviewed fabrication methods of CNTs. In this subsection, we
briefly explain characteristics of CNTs, especially optical characteristics.
CNTs typically have 0.6 ~ 2 nm diameter and 1 µm length so that they have nearly identical
1D structures. CNT structures and their physical properties are determined by their
diameter and chiral angle (rolling direction of graphene sheet). Fig. 1 shows an unrolled
hexagonal lattice of a CNT, a graphene sheet. The chiral vector (Ch) connects the two points

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Optical Deposition of Carbon Nanotubesfor Fiber-based Device Fabrication 387

which become the identical point when we roll up the sheet to make it a cylinder, or a CNT.
The vector is called the “chiral vector”.
The chiral vector (Ch) is expressed using unit vectors a1 and a2 and two integers n and m (0 ≤
m ≤ n) as

C h = na1 + ma 2 ≡ (n, m) (1)

The type of CNT is completely determined by the two integers (n,m) through the definition
given in Eq. (1). For example, (6,2) chiral vector is shown in Fig. 1. Originating from their 1D
structure, wave vectors of CNTs are discretely existing. This discretion form a sharp
divergence in their electron density of state (eDOS), called “van Hove singularities,” that is
typical characteristic of 1D materials.
Their eDOS structures are determined by their chirality. We can classify CNTs into two
groups, metallic and semiconducting. In general, mod(n−m, 3) = 0 CNTs are metallic and
mod(n−m, 3) ≠ 0 CNTs are semiconducting. One of the most important characteristics of
CNTs is that the difference between metallic and semiconducting properties is determined
by their chirality.

Chiral Vector (n,m)

Ex. (6,2)

a2 Ch

a1
Two fundamental vectors
Fig. 1. Schematics of 2D graphene sheet
Semiconducting CNTs absorb the light whose energies are same as their bandgaps. The
bandgap energies are controllable by choosing appropriate CNTs diameter, since the
bandgap energies are almost inversely proportional to their diameters. The CNTs work as
saturable absorbers in the absorption band. Saturable absorbers are materials or devices
which change their absorbance depends on power of incident light. They absorb the light
which has low intensity, whereas the absorbance decreases due to the saturation of
absorption in the case of high intensity light. This phenomenon can be understood as eDOS
occupation in conduction bands of saturable absorber material (Fig. 2). If the low intensity
light incidents, electrons in valence band are excited up to conduction band, and photons
are highly absorbed. On the other hand, if the optical intensity is high, some photons are not
absorbed because the eDOS in conduction band is occupied with other electrons which
excited by the light. Thus, the optical intensity dependent transparency, the saturable
absorption reveals.
This kind of intensity dependent attenuation enables the high-intensity components of an
optical pulse to pass through saturable absorbers, while the lower intensity components of
the pulse, such as the pulse wings, pedestals, and background CW radiation, not to pass

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388 Frontiers in Guided Wave Optics and Optoelectronics

Saturable Vacant
Absorber Ec

Low Intensity Photon Ev

High Loss
Occupied
Ec

High Intensity Photon

Ev

Low Loss
Fig. 2. Schematics of saturable absorption (Ev and Ec denotes energy levels of valence band
and conduction band, respectively)
(Fig. 3). When a saturable absorber is inserted in a laser cavity, amplified spontaneous
emission (ASE) noise of a gain medium is shaped to be a pulse train. In every round trip,
light pass the saturable absorber as high intensity noise with low loss and low intensity
noise with high loss, resulting in high intensity contrast. Finally, light start to oscillate in
pulsed state.

Gain Medium

Output
Saturable Absorber

Round Round pulse

ASE trip trip

Fig. 3. Schematics of noise suppression by saturable absorber

For ultrashort pulse generation, a saturable absorber with a fast recovery time is required for
stabilizing laser mode-locking, while a slower recovery time could facilitate laser self-
starting. Recovery time of CNTs have been measured to be shorter than 1 ps, and CNTs are
suitable material for ultrashort pulse generation. However, the recovery time of CNTs only

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Optical Deposition of Carbon Nanotubesfor Fiber-based Device Fabrication 389

consisted by semiconducting CNTs is not so fast (around 30 ps) (Rubtsov et al., 2004). The
ultrafast response time of CNTs are based on bundles and/or entanglements of
semiconducting and metallic CNTs because the electrons which are excited by photons in
semiconducting CNTs couple to metallic CNTs, resulting in ultrafast recovery time of
semiconducting CNTs. As-synthesized CNT samples consist of CNTs which have several
different chiralities, including both metallic and semiconducting CNTs. Therefore, the CNT
samples inherently have ultrafast recovery time shorter than 1 ps.
It is difficult to selectively fabricate CNTs which have certain chirality. However, the
mixture of several types of CNTs have two advantages. One of the advantages is ultrashort
recovery time which we mentioned above. Another advantage is its wide absorption band.
Different chiralities of CNTs have different absorption band, and, consequently, their
mixture effectively has very wide absorption band. The wide saturable absorption band is
required for passively mode-locked laser whose output pulse width is ultrashort, such as
femtosecond regime.

2.3 CNT based optical device structures and fabrication methods

After CNT optical devices were first demonstrated, three types of CNTs based device
structures have been proposed. They are depicted in Fig. 4, transmission type, reflection
type and fiber end type. These device structures were confirmed to have good performance
to provide CNT-based optical devices. However, the fabrication process had some problems
in terms of efficiency.
The three types of devices was first fabricated and demonstrated by spraying method (Set
et al., 2004a; Set et al., 2004b). The spraying method is common method to evaluate and
characterize CNT samples. In the method, we first prepare a CNT-dispersed solution. CNTs
tend to be entangled with each other, and few kinds of solvents can be used to disperse
them in high uniformity and fewer entanglements. DMF is one of the most commonly used
solvents where CNTs can be dispersed. After the preparation, we spray substrates and fiber
ends with the solution, and evaporate the residual DMF by heat. The largest advantage of
this method is simplicity: we can fabricate optical devices using simple setup. However, the
efficiency of CNT-use is poor. The sprayed solution spread around the target position where
we want to deposit CNTs.

Transmission Type Reflection Type Fiber End Type

In In In Out

Out Out

mirror mirror fiber fiber

In In In In
In In
Out Out Out Out
Out Out
CNT substrate CNT CNT CNT CNT
CNT
embedded embedded embedded

Fig. 4. Schematics of three types of carbon nanotubes optical devices

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390 Frontiers in Guided Wave Optics and Optoelectronics

After the proposal, direct synthesis method (Yamashita et al., 2004) and polymer embedding
method (Sakakibara et al., 2005) have been reported. Though embedding CNTs into
polymer materials have been already demonstrated (Sakakibara et al., 2003), the report was
the first application to the passive mode-locker in the fiber-end-type configuration. The
polymer embedding method can remove the impurities before embedding CNTs into
polymer materials. The method requires setups for polymer material processing, and the
large number of CNTs is not settled through optical pass of devices. In the direct synthesis
method, CNTs were directly synthesized onto optical fiber ends, and the fiber produced
passively mode-locking of a fiber laser. However, there is no method to remove impurities
in as-synthesized CNTs, and consequently ultra-high performance CNT fabrication setup is
required.
From the next section, we show our proposal of optical deposition of CNTs. Our proposal
offers very simple CNT-based optical device fabrication method, and efficiency of CNT-use
drastically increases.

3. Optical deposition of carbon nanotubes

3.1 Optical deposition of carbon nanotubes onto fiber ends
There is a problem in handling CNTs because CNTs tend to entangle with each other and
they are difficult to be dispersed in common solvents. In optical device applications, CNTs
are conventionally used by spraying, directly synthesizing onto a device, or embedding into
a polymer material. These processes are mostly complicated, large-scale setups are required
and CNTs are not efficiently used in these methods. To minimize the dissipation number of
CNTs, we have proposed and demonstrated optical deposition of CNTs. The method
enables area-selective deposition of CNTs only onto a core region of an optical fiber end.
This technique will drastically improve the efficiency of CNT usage and the fabrication costs
of CNT-based photonic devices.
Our experimental setup is very simple as shown in Fig. 5. It is composed of just two
equipments, a laser diode and an erbium doped fiber amplifier (EDFA). We first prepared a
purified CNT-dispersed DMF solution. Light produced from a laser diode which had the
wavelength of 1560 nm and the optical power of -10 dBm was amplified upto about 20 dBm
by a high-power EDFA. The light was incident into the solution through a cleaved fiber end.
We observed CNT deposition conditions on the fiber end facets using a microscope for
several different optical powers. Microscopic Raman spectroscopy was used to confirm the
existence of CNTs at selected area. To find the dependence of the numerical aperture (NA)
of the optical fiber, we used two types of optical fibers having different NAs, single-mode
fibers (SMFs) and dispersion-shifted fibers (DSFs).

Cleaved Light
LD
Fiber End
1560nm 30dBm
-10dBm EDFA

CNTs dispersed
DMF Solution CNTs Bundle
Fig. 5. Experimental setup for optically depositing carbon nanotubes onto fiber end

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Optical Deposition of Carbon Nanotubesfor Fiber-based Device Fabrication 391

(a1) (b1) (c1)

Core Core Core

Cladding Cladding Cladding
35000 80000 80000
Intensity [arb. unit]

Intensity [arb. unit]

Intensity [arb. unit]

30000 (a2) (b2) (c2)

25000 60000 60000
20000
40000 40000
15000
10000 20000 20000
5000
0 0 0
0 500 1000 1500 2000 0 500 1000 1500 2000 0 500 1000 1500 2000
Raman shift [cm-1] Raman shift [cm-1] Raman shift [cm-1]

Fig. 6. Microscope images and Raman spectra of CNT-deposited SMF ends. Injected light
power: (a) 20.0, (b) 21.5, and (c) 22.0 dBm.
In Fig. 6, microscope images and Raman spectra of CNTs deposited fiber ends of standard
SMFs are shown. Fig. 6 (a), (b), (c) correspond to incident optical power of 20 dBm, 21.5 dBm
and 22.0 dBm, respectively. Solid circles in Fig. 6 (a1), (b1), (c1) indicate core areas of SMFs,
and corresponding Raman spectra are shown with solid curves in Fig. 6 (a2), (b2), (c2).
Broken circles are the areas where CNTs are deposited outside of the core, and
corresponding Raman spectra are shown with broken curves.
There are three major peaks in the Raman spectra of CNTs. The most typical peak of CNT
appears at around 250 cm-1, and it due to the radial breathing mode (RBM), which is a
vibration mode of CNTs in the radial direction. We confirmed the presence of CNTs from
the peak. The optical power of 20.0 dBm was not enough to trap the CNTs, whereas Fig. 6
(a) shows the existence of CNTs that may be accordingly attached to the cladding region of
the fiber end. In Fig. 6 (b), CNTs were area-selectively deposited onto the fiber end only on
the core region, and the Raman spectrum shows the existence of CNTs. By increasing the
optical power up to 22.0 dBm, CNTs were not deposited onto the core region but deposited
around the core.
In the case of DSF, an optical power of 19.0 dBm was enough to deposit CNTs. Fig. 7 shows
a microscope image of the fiber end facet and its Raman spectrum at the core center. By
increasing the optical power up to 21.5 dBm, CNTs were deposited around the core.
Stronger confinement of light in DSF reduced the required optical power for CNT
deposition by 2.5 dB, and widened the margin to ±2 dB.
The principle of this technique is not yet confirmed, but we presume that one possible
mechanism is the optical tweezer effect, which is caused by the optical intensity diversion of
the light in a solution. Another possible mechanism would be the flow of solution due to the
injected light. The light might thermally induce convection and swirl nearby the core, and
entangled CNTs were attached.
It is possible to deposit CNTs onto a fiber ferrule end as shown in Fig. 8. We deposited
CNTs onto an end facet of a standard SMF with a ferrule using an optical intensity of 21.5

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392 Frontiers in Guided Wave Optics and Optoelectronics

dBm, which is the same experimental condition as that of the fiber shown in Fig. 6 (b).
Raman spectra in Fig. 8 show that CNTs were area selectively deposited only onto the core
region. This technique will reduce the alignment cost after CNT deposition.

Core
Cladding
40000

Intensity [arb. unit]

30000

20000

10000

0
0 500 1000 1500 2000
Raman shift [cm-1]
Fig. 7. Microscope image and Raman spectrum of CNTs deposited onto DSF end using 19.0
dBm injected light.
Core
Cladding
Intensity [arb.unit]

50000
40000
30000
20000
10000
0
0 500 1000 1500 2000
Raman shift [cm-1]
Fig. 8. Microscope image and Raman spectrum of CNT-deposited SMF end with ferrule
using 21.5 dBm injection light.

3.2 Passive mode locking of fiber laser using optically deposited CNTs
In previous subsection, we have explained the method to deposit CNTs only onto the core
region of optical fiber ends. We have deposited CNTs onto optical fiber end with ferrule
intended to use as a saturable absorber. In this subsection, to ensure that the performance of
the technique is sufficient for fabricating optical devices, we report a passively mode-locked
fiber laser that employs the fiber, which had optically deposited CNTs on its fiber end.
The experimental setup is shown in Fig. 9. An EDFA was used as the laser gain medium and
an isolator was inserted to prevent back reflection in the cavity to ensure one-directional
lasing. We controlled the polarization state using a polarization controller (PC). The total
dispersion in the laser cavity was adjusted to be nearly zero by inserting a 20-m-long SMF.
The output light came out from a 3 dB coupler. A CNT-deposited fiber on its end with
ferrule was inserted as an alignment-free passive mode-locker. The insertion loss of the fiber
was about 4.2 dB. We measured an optical spectrum using an optical spectrum analyzer and
an autocorrelation trace using a second-harmonic generation (SHG) autocorrelator.

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Optical Deposition of Carbon Nanotubesfor Fiber-based Device Fabrication 393

By injecting 200 mA to the pump laser of the EDFA and controlling the polarization state of
the light inside the laser cavity, we achieved passively mode-locked oscillation. An optical
spectrum of the laser output measured with a 0.1 nm resolution is shown in Fig. 10 (a). The 3
dB spectral width was 3.2 nm. The SHG autocorrelation trace with a 50 fs resolution is
shown in Fig. 10 (b) and had a full-width at half-maximum (FWHM) of 630 fs. Assuming a
transform-limited sech2 pulse waveform, the pulse width is calculated to be as short as 400
fs. The pulse width was almost independent of EDFA gain and was highly dependent on the
dispersion of the laser cavity.

PC
EDFA
Isolator
3 dB SMF 20 m
Coupler

Sleeve
Output
Fiber
Ferrule CNT layer

Fig. 9. Experimental setup for passively mode-locked fiber laser using a CNT-deposited
fiber as a saturable absorber.

-10 1.2
(a) 3.2nm (b)
1.0 Sech2 400fs
Output power [dBm]

Intensity [arb.unit]

-20 0.8
630fs
0.6
-30
0.4

-40 0.2
0.0
-50 -0.2
1547 1552 1557 1562 1567 -2 -1 0 1 2
Wavelength [nm] Delay [ps]

Fig. 10. Optical output characteristics of passively mode-locked fiber laser in Fig. 9 (a)
Optical spectrum (resolution 0.1 nm). (b) SHG autocorrelation trace (resolution 50 fs).

4. In-situ monitoring of optical deposition of carbon nanotubes onto fiber end

The method described in the previous section requires only a lightsource to deposit CNTs
onto a core region of an optical fiber end. Light injection from the fiber end into CNT-
dispersed solution preferentially deposits CNTs onto core regions of optical fiber ends,
resulting in efficient CNT-use. Optical pass alignment, therefore, is not necessary for this
technique.
However, the technique requires very precise control of the light injection power to deposit
uniform and less scattering CNT layer because highly uniform CNT solution, which has

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394 Frontiers in Guided Wave Optics and Optoelectronics

very small CNT entanglements, is required. Smaller CNT entanglements require higher
injection power. With the increase of the light intensity, flow induced by the light injection
becomes too high speed to trap the CNTs onto the core. High power injection deposits CNTs
around the core, not on the core, as we have already depicted in Fig. 6. The upper limit of
optical intensity depends on the flow speed caused by the injected light. Additional
technique is, accordingly, needed to optimize injection power for each solution. In this
section, we employed optical reflectometry to simplify the optimization process and deposit
CNTs onto very small areas.
The experimental setup for the in-situ optical reflectometry is shown in Fig. 11. Light at a
wavelength of 1560 nm from a laser diode was used for both the optical deposition and the
optical reflectometry. The light was amplified by a high-power EDFA, and subsequently
was split into two by a 10:90 coupler. The 10 % of the light was monitored for reference by a
power meter after 20 dB attenuation. The light of 90 % was injected from a cleaved fiber end
into a DMF solution, where purified CNTs were uniformly dispersed. The power of the
reflected light from the fiber end was measured by another power meter through a
circulator. The reference and the reflected light powers were measured at every 500 msec.
The refractive indices of DMF and silica-glass are 1.42 and 1.44, respectively. Since the
refractive index difference between DMF and silica-glass was small, the reflection was
suppressed before CNT deposition. On the contrary, semiconducting CNTs had the
refractive indecies of around 3.0, though the refractive indecies of CNTs depend on their
chiralities(Margulis & Gaiduk, 2001).
The reflectivity drastically increased after the first deposition of an entanglement. The
deposition was achieved by the optimization of the injection power with monitoring the
reflection. Even if we repeat the experiment by changing the injection power with the highly
uniform CNT solution, we could not deposit the CNTs only onto the core without the
reflectometry. It was because there was very small margin of the injection power when we
used the highly uniform CNT solution. Moreover, the solution condition, especially the sizes
of the CNT bundles, changed in time and this prevented us from the preferential deposition
without the reflectoemtry. The optical reflectometry offered the detection capability of the
starting time of CNT deposition to the system and, consequently, controllability of the
number of CNTs by adjusting the light injection duration after the deposition started.
Subsequent to the process, we took microscope images and field emission scanning electron
microscope (FE-SEM) images of the fiber ends.
Light
High power
EDFA Cleaved
90% fiber end
LD

1560nm 10%
-10dBm 20dB Att. Power
meter
Power
meter CNT dispersed CNT
solution (DMF) entanglement

Fig. 11. Experimental setup for optically manipulated CNT deposition with optical
reflectometry monitoring.

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Optical Deposition of Carbon Nanotubesfor Fiber-based Device Fabrication 395

Fig. 12 shows in-situ optical reflectometry data series which describe the deposition
processes of thin and thick layers. Once the EDFA was turned on, its output was kept
constant around at 20 dBm. It took a short period of time (10 - 100 s) to start the deposition.
The start times were not the same in the two cases because the solution was not completely
uniform. The reflectivity was as small as -40 dB because of the small refractive index
difference between DMF and the fiber. Fig. 12 clearly show the drastic increase of the
reflectivities about 20 dB due to the first entanglement deposition. The thicknesses were
controlled by changing the light injection period after the increase of reflectivity. To deposit
a thin layer, the EDFA was turned off at 8 seconds after the start of deposition as shown in
Fig. 12 (a). In the case of the thick layer deposition, the EDFA kept on for about 4 minutes
after the deposition starting. During the deposition, the fluctuation of reflectivity gradually
decreased (Fig. 12 (b)). It indicates that the CNT layer gradually became uniform.
The introduction of optical reflectometry produced important functionalities to the system:
deposition starting time detection and in-situ layer uniformity evaluation. The thickness of
CNT layer could be roughly adjusted by controlling duration of injection even without the
reflectometry. Since entangled CNTs which flowed to a fiber end were trapped and
deposited, CNT deposition did not start just after the light injection. This was the reason
why it was difficult to control the number of CNTs. First deposition of CNT entanglement
drastically increased reflectivity at the fiber end due to the high index contrast between
CNTs and silica-glass. It, then, became a seed of a CNT layer and the deposition continued
because of strong Van der Waals force among CNTs. The duration of the deposition,
therefore, controlled the layer thickness by introducing optical reflectometry. As the layer
became more uniform, the reflection became less affected by the solution flow. The
fluctuation of the reflectivity gradually decreased.
Optical microscope images of the thin and thick layers are shown in Fig. 13. The figures
describe the thickness difference between the two layers. To directly observe the existence of
CNTs, the layer thicknesses and the sizes of the deposition regions, we took the FE-SEM
images of the fiber ends shown in Fig. 14 and Fig. 15. The thin CNT layer was clearly
observed only at the core region in Fig. 14, whereas the deposited layer was very thick in
Fig. 15. The thick layer was preferentially deposited only onto ~15 μm diameter circular
region. This result was achieved using the highly uniform solution solution and the precise
optimization of injection power which was enabled by the in-situ optical reflectometry.

Reflectivity Input power Reflectivity Input power

EDFA on EDFA off EDFA on EDFA off
0 30 0 30
Input Power [dBm]
Input Power [dBm]

-10 20 -10 20
Reflectivity [dB]
Reflectivity [dB]

-20 10 -20 10
-30 0 -30 0
-40 -10 -40 -10
-50 Deposition start -20 -50 -20
Deposition start
-60 -30 -60 -30
0 5 10 15 20 25 30 0 100 200 300 400
(a) Time [s] (b) Time [s]
Fig. 12. Data series of optical reflectometry of CNT deposition (a)thin layer deposition
process (b)thick layer deposition process.

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396 Frontiers in Guided Wave Optics and Optoelectronics

(a) (b)
Fig. 13. Optical microscope images of fiber ends with CNT layers on the core region (a) thin
CNT layer (b) thick CNT layer.

10μm 1μm
(a) (b)
Fig. 14. FE-SEM images of the fiber end with the thin layer (a) whole fiber end
(b) magnified around the core region

~15μm

10μm 1μm
(a) (b)
Fig. 15. FE-SEM images of the fiber end with the thick layer (a) whole fiber end
(b) magnified around the core region.

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Optical Deposition of Carbon Nanotubesfor Fiber-based Device Fabrication 397

5. Optical deposition of CNTs around microfiber

In section 3 and 4, we reported the optical deposition of CNTs onto the optical fiber ends. In
this section, we show one aspect of versatility of the deposition method, CNT deposition
around a microfiber. Evanescent coupling between CNTs and propagation mode of a
microfiber is one way to realize polarization insensitve CNT device as already reported
(Kieu & Mansuripur, 2007; Song et al., 2007).
First, we fabricated a microfiber using an experimental setup shown in Fig. 16. A bare
standard single mode fiber (SMF) was set on two fiber holders, which were fixed on two
translation stages. The fiber ends were connected to an erbium doped fiber amplifier
(EDFA) and a power meter, respectively. We fabricated a microfiber by stretching the fiber
with heat produced by a flame. During the fabrication process, we monitored the insertion
loss of the fiber using the power meter. The fiber was tapered down so that its taper waist
diameter became ~6 μm.
Fiber holder Bare SMF
Stretch Stretch
Power
meter
EDFA
Flame
Translation stage

Fig. 16. Schematic of fabrication of microfiber

Next, we deposited CNTs around the microfiber using a setup shown in Fig. 17. The
fabricated microfiber was immersed into a CNT-dispersed DMF droplet on a slide glass.
Light from a laser diode at a wavelength of 1560 nm and at -10 dBm optical power was
amplified up to 13 dBm by an EDFA and consequently injected into the microfiber. The
output power was monitored by a power meter to detect start of CNT deposition, and
consequently to control the deposition time.
CNT dispersed
DMF droplet
EDFA Taper Microfiber
LD Power
meter
1560nm Slide
13dBm
-10dBm glass
Fig. 17. Schematic of optical deposition of CNT around microfiber
Fig. 18 (a) shows a microscope image of a CNT-deposited microfiber, whose waist diameter
was ~6 μm. We found that the CNTs start to be deposited around the microfiber at the incident
power of 13 dBm. To ensure the existence of CNTs, we performed microscopic Raman
spectroscopy. The dotted circle in Fig. 18 (a) was the area where microscopic Raman
spectroscopy was performed. The microscopic Raman spectrum in Fig. 18 (b) confirms that the
CNTs were certainly deposited around the microfiber. The optical deposition technique was
confirmed to be applicable not only to deposition onto fiber ends but also to deposition around
microfibers. We could detect the start of the CNT deposition by the drop of the output power
due to scattering and absorption induced by deposited CNTs. We stopped the light injection
about 5 sec after the deposition started. The excess loss induced by the tapering was 0.2 dB.
The CNT deposition increased insertion loss by 5.8 dB and the total loss was 6 dB.

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398 Frontiers in Guided Wave Optics and Optoelectronics

70000

60000 (b)
(a) G-Band

Intensity [a.u.]
50000
CNTs ~6μm 40000

30000 RBM SiO2 D-Band

20000

10000

0
Microfiber 0 200 400 600 800 1000 1200 1400 1600 1800

Raman shift [cm-1]

Fig. 18. (a) Microscope image of CNT-deposited microfiber (waist ~6 μm), dotted circle
indicates area where microscopic Raman spectrum was measured, (b) Microscopic Raman
spectrum of CNT-deposited microfiber.
We presume the similar phenomenon occurred both in the case of optical CNT deposition
onto fiber ends and around microfibers. In the case of the CNT deposition onto fiber ends,
swirl and convection caused by the light injection to a CNT-dispersed solution might
deposit CNTs. The deposition mechanism might be the combination of the convection and
the optical tweezer effect. On the contrary, in the present experiment, the light injection
from air into the droplet thermally caused swirl and convection at the boundary. The swirl
and convection induced by the light injection might deposit the CNTs around the
microfibers. This phenomenon occurs only at the light input side boundary, and enables us
to area-selectively deposit them onto desired position. Another possible mechanism is the
optical tweezer effect, which can traps micro- and nano-sized objects by the optical intensity
diversion in the solution. Evanescent field had the optical intensity diversion, and mode
field mismatch between the air section and the DMF section caused the optical intensity
diversion by scattering. The diversion might trap the CNTs and deposited onto the
microfiber.
In order to confirm the saturable absorption property of the fabricated device, we applied it
to mode-lock a fiber laser. We inserted the fiber, mentioned above, in a fiber laser cavity to
achieve a passive mode-locking. The experimental setup is shown in Fig. 19. An EDFA
produced gain of the laser. The polarization state inside the laser cavity was controlled by a
polarization controller (PC). An isolator eliminated back-reflection inside the laser cavity,
mainly occurred at the tapering region and the CNT-deposited part. The laser output came
out from a 10% port of a 10:90 coupler. We measured optical spectrum and second harmonic
generation (SHG) autocorrelation trace of the laser output using an optical spectrum
analyzer and a SHG autocorrelator. We measured pulse repetition rate using a photodiode
and an oscilloscope.
Fig. 20 shows an optical spectrum, an autocorrelation trace and a pulse train of the fiber
laser output. The laser had the center wavelength at 1565 nm and the 3-dB bandwidth of 3.7
nm. The full width half maximum (FWHM) of the autocorrelation trace was 1.61 ps, which
correspond to inferred pulse duration of 1.14 ps (assuming Gaussian pulse profile). The time
bandwidth product (TBP) of the pulse was 0.528. Comparing to an unchirped transform-
limited value of Gaussian pulse (0.441), the result indicates the pulse had chirp. The chirp
was due to the residual dispersion in the laser cavity. The repetition rate of the fiber laser
was 1.54 MHz according to the time interval of the output pulse train.

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Optical Deposition of Carbon Nanotubesfor Fiber-based Device Fabrication 399

Polarization controller

EDFA
Isolator
90
Taper CNT
10 Output

Microfiber
Fig. 19. Schematic of a passively mode-locked fiber laser using a CNT-deposited microfiber.

-10 1.2
3.7nm (b)
-20 (a) 1.0
Intensity [a.u.]
Output [dBm]

-30 0.8
1.61ps
-40 0.6
-50 0.4
-60 0.2
-70 0.0
-80 -0.2
1545 1555 1565 1575 1585 -3 -2 -1 0 1 2 3
Wavelength [nm] Time delay [ps]

1.2
1.0
(c)
650ns Col 1 vs Col 2
Voltage [V]

0.8
0.6
0.4
0.2
0.0
-1.0 -0.5 0.0 0.5 1.0
Time [μs]
Fig. 20. Passively mode-locked fiber laser output (a) Optical spectrum of the fiber laser
(resolution: 0.1 nm) (b) Autocorrelation trace of laser output (resolution: 50 fs,)
corresponding pulse width: 1.14 ps (assuming Gaussian pulse) (c) Output pulse train of the
fiber laser (repetition rate: 1.54 MHz)

6. Conclusion
In this chapter, we have proposed and demonstrated the optical deposition method of
CNTs. After brief introduction of this chapter (section 1), we explained the general
characteristics, optical properties, and optical devices based on CNTs in section 2. From

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400 Frontiers in Guided Wave Optics and Optoelectronics

section 3, we reported optical deposition of CNTs. In section 3, we deposited CNTs by

injected light from the optical fiber end into a CNT-dispersed solution. In subsection 3.1, we
area-selectively deposited CNTs only onto the core region of optical fiber ends, such as a
bare SMF and a bare DSF, by controlling the injection power. The area-selectivity was
confirmed by microscopic Raman spectroscopy. A SMF with ferrule could be used as a
deposition object, and it produced passive mode-locking of a fiber laser after the deposition
(subsection 3.2).
The result confirmed the technique to have good performance of CNT-based device
fabrication. However, the result showed that we need strict power control of the injection
light within 2 dB for SMF. To solve this problem, we employed optical reflectometry into the
method for in-situ monitoring of the deposition in section 4. The reflectometry offered easy
optimization method for the injection power control. We deposited CNTs onto very small
area (~15 μm diameter circular region) using highly uniform CNT-dispersed solution.
In section 5, we showed that the optical deposition method was also applicable to
microfibers. We achieved CNT deposition around a microfiber, which were immersed in a
CNT-dispersed DMF droplet, by injecting light through the microfiber. We confirmed the
fiber could be used as a passive mode-locker in a fiber ring laser.
We believe our proposed method, optical deposition of CNTs, will contribute to
development of ultrafast photonic applications based on CNTs in device fabrication aspect.

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 Frontiers in Guided Wave Optics and Optoelectronics
Edited by Bishnu Pal

ISBN 978-953-7619-82-4
Hard cover, 674 pages
Publisher InTech
Published online 01, February, 2010
Published in print edition February, 2010

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