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Fabrication of carbon nanotube on silicon (CNT on Si) high

resolution AFM tips: a chronological view

(indice)

1. Introduction: Purpose of CNT AFM tips


Since their discovery in 1991 4, carbon nanotubes (CNTs) have been a
discovery of great interest due to their unique properties and their wide
diversity of applications, including probe tips for scanning probe microscopy
(SPM) 1.
Among other applications in this field, the use of CNT in scanning probe
microscopy (mainly AFM) (CNT/AFM probes) have been proved to display a
better high-resolution imaging when compared to silicon probes, since this
kind of probes feature special properties such as a smaller tube diameter
(less than 10 nm, which significantly improves their lateral resolution as
opposed to conventional silicon probes), a higher aspect ratio (between 10
and 1000, which makes it possible to probe deep and steep features) 2 ; a
high chemical stability and stiffness and, whats most important, an elastic
buckling when contacting the sample 4. On top of that, since molecular
structures of CNT are well defined, theoretically it will be possible to make a
batch of nanotube tips where all of them have identical structure and
resolution.
.Several

methods have been developed over time to fabricate CNTs onto


AFM probes in a way that can be controlled as much as possible. All these
fabrication process will start with a classic silicon AFM tip (a microfabricated
silicon or silicon nitride cantilever with an integrated pyramidal tip 3) and will

end with the same tip covered in carbon nanotubes presenting some kind of
arrangement that we will discuss later.
2. Some previous concepts
2.1 Types of nanotubes
When fabricating carbon nanotubes, we can find several kinds of them:
Single-wall nanotubes (SWNT) are tubes of graphite which structure can be
visualized as a layer of graphene which is rolled into a seamless cylinder.
They are more pliable than MWNT but it is harder to make them. They can
be twisted, flattened, and bent without breaking.
Multi-wall nanotubes (MWNT) are tubes of graphite that can the form of a
coaxial assembly of SWNT s of different diameter, or of a scroll of a single
sheet of graphene. MWNT are easier to produce in high volume quantities
than SWNT. However, the structure of MWNT is less well understood due to
its complexity.
Double wall nanotubes (DWNT) are a midpoint between SWNTs and MWNTs.
It is a coaxial assembly of two SWNTs.
All three kinds are represented in the Figure 2.1:

a)

b)

c)

Figure 2.1: a) SWNT. b) DWNT. c) MWNT

2.2 First use of CNT as SPM probes


In 1996, first attempts of SPM probes with CNT were made by Hongjie et al.
1
. This research was made in order to solve the problem of tip crash
problems due to the use of brittle tips such as the classical pyramidal silicon
AFM tips; as well as the inability to know the atomic configuration of the tip
during imaging accurately.
One of the main reasons why CNT were so relevant for this purpose is that
this kind of tip has the unusual property of being both stiff and gentle. It is
stiff because there is no bending of the nanotube at all when it encounters a
surface at near-normal incidence until the Euler buckling force,
exceeded 1. This force can be expressed as:

F EULER , is

F EULER=

Where

YI
L2

is the Youngs modulus,

the cross-section of the nanotube and

is the bending stress moment over

is the length of the nanotube.

When that force is exceeded, the nanotube will start to bend. In this
particular study,

F EULER is estimated to be

5 nN, much gentler than the

maximal force a pyramidal silicon tip can exert when tapping a sample if the
experiment is not carefully controlled, which is

100

nN. This is quite

important as it can prevent damage to delicate organic and biological


samples 2.
The tip fabrication method for these initial experiments was simple: The
bottom section (1-2 m) of the tip was coated with an acrylic adhesive by
sticking it into an adhesive-coated carbon tape. Then this adhesive-coated
tip made contact with the side of a bundle of 5-10 MWNTs while being
observed with dark-field optical microscopy 1. Once attached, the nanotube
bundle was pulled from its neighbouring nanotubes leaving a single MWNT
at the end of the tip. An image of these initial tips can be seen in Figure ().

Figure (): First fabrication of a CNT AFM tip. The selected area corresponds approximately to
the coated region of the silicon tip, the nanotube bundle attached to it and the single MWNT
at the end of the tip.

Besides being proved to have an equal or better resolution when compared


to silicon tips, another interesting property showed by these kinds of tips is
their great thinness at their apex, which provides a better imaging at small
gaps where a silicon tip would not be accurate enough. For example, when
fabricating these tips a 400 nm wide, 800 nm deep trench etched in a TiNcoated Si wafer was imaged, confirming this statement. As we can see in
Figure (), the silicon tip did not reach the bottom and imaged a triangular
valley, which is consistent with a imaging artefact caused by the pyramidal

shape of the tip. On the other hand, the CNT tip was able to reach the
bottom of the trench and even image the texture of it:

Figure (): a) Image of the abovementioned trench using a Si tip. b) Image


using a CNT tip. c) Texture of the bottom of the trench as imaged by the CNT
tip.
2. Early attempts of fabrication
These CNT sticking to Si tip methods were the first to be developed for this
kind of fabrication. The main problem with the method used by Hongjie et
al. was that, with that procedure it was difficult to adjust the length of the
nanotube tip and to obtain a strong and reliable attachment. In 1999
Nishijima et al. 2 found a way to improve both of these problems.
For this fabrication method, previously prepared nanotubes were
ultrasonically dispersed in isopropyl alcohol and then this suspension was
centrifuged in order to remove larger particles.
The nanotube solution was thereupon deposited on a 500 m gap between
the knife edges of two disposable razors, on a glass plate; and they were
subsequently aligned by an ac electrophoresis technique. When applying
the ac field, the nanotubes were separated from nanoparticles present in
the solution and moved to the knife edges while being oriented parallel to
the electric field. When the solvent evaporated, they remained fixed in that
position by Van der Waals forces, solving one of the problems presented by
the previous method.
One of the aligned nanotubes located on the knife edge was transferred to a
silicon tip by applying a dc bias voltage between the two of them, using a
SEM to know where the nanotube had been transferred on the tip.
Finally, the nanotube was attached to the Si tip by amorphous carbon
deposition; which was performed by the dissociation of contaminants
(mainly hydrocarbons) by the electron beam of the SEM mentioned above.
An image of the finished tip can be seen in Figure ().

Figure (): CNT/Si tip obtained with this method. The highlighted area indicates where
the nanotube tip is located.

Again, this method had proven to produce tips that reach higher lateral
resolutions than the conventional tips, this time by imaging DNA and
comparing the results obtained. (figure optional).
This method has been used for quite some time ever since. For example, it
was the method used in 2006 for the fabrication of SWNT, MWNT and DWNT
tips in order to compare their performance.
Other contemporary early attempts of fabrication included, for example, the
creation of a MWNT cartridge by chemical vapour deposition (CVD) and the
subsequent transference of the nanotubes from the cartridge to the silicon
tip using an electric field.
3. Refining the method: the direct chemical vapour deposition
Even though some of the initial problems had been solved by this time,
there were still some major issues at stake, some of which could be avoided
quite easily. First of all, the use of a SEM limited the minimum size of the
bundles or nanotubes to the minimum size the SEM could distinguish
(typically between 5 and 10 nm), which affected the lateral resolution of the
tip directly. Second, the attachment time between a nanotube and a tip was
relatively long. And third, there are no well defined and reproducible etching
procedures accurate enough to expose a single nanotube.
In order to solve these issues, and given that there was a technique to
grow nanotubes by CVD (as seen in the creation of a MWNT cartridge in the
last section), a method to grow them directly on commercial tips.
Furthermore, by changing certain parameters (which will be discussed
below), either MWNT or SWNT tips would be fabricated.
In this method, shown schematically in Figure (), first a flattened area was
created at the tip. With the help of an optical microscope, the apex of the tip
was placed in a drop of HF solution between two wires acting as counter
electrodes, and it was subsequently anodized when a difference of potential

is applied between the two electrodes. Then, anodized tips were etched in a
KOH solution. This whole procedure etched 100 nm diameter, 1 m deep
pores.
Then, for MWNT tips, an iron catalyst was electrochemically deposited into
the pores, under de view of an optical microscope. Here,

M H2 S O4

MFeS O4

and

was used. Later, they were oxidized and then heated in a

furnace at 800C in a flow of argon and hydrogen, and a flow of ethylene (

C2 H 4 ) was added for 10 minutes to grow the nanotubes.

Figure (): Schema of the fabrication procedure for this CVD method

On the other hand, SWNT tips were prepared in a similar manner but, to
favour the growth of SWNTs, colloidal

Fe Ox

nanoparticles were used as

the CVD catalyst instead of the previous solution, since the particle size was
comparable to the desired nanotube diameter. They were electrophoretically
deposited as well; and the SWNT were grown in similar conditions to those
of MWNT.
4. Batch production: CVD and the dielectrophoretic method
Up until this point, all possible fabrication methods had been one-by-one
procedures, which was a big issue to fix. The previous CVD method had
been used for batch production, but the main problem with this method was
that thermal CVD growth has very little control over the CNT location,
density length and orientation 4. It was really difficult to obtain individual,
well-oriented MWNTs using thermal CVD. The rate of usable tips was thus
very low; and even then, at the end of the fabrication most tips still required
a one-at-a-time manipulation to remove extra CNTs or to shorten the
remaining CNTs.
With the objective of avoiding these problems, a bottom-up wafer scale
fabrication method was developed in 2004 4; combining nanopatterning and
nanomaterials synthesis with the silicon cantilever microfabrication
technology used for the classical fabrication of tips:

Figure (): Schema of the fabrication process

The fabrication process, which is shown schematically in Figure (), consisted


of 5 major steps:
First of all, the SOI sample was coated with an electron beam (e-beam)
resist (in this case, PMMA) and this resist was subsequently developed
through e-beam lithography, creating several dots (gaps) on it that would
become the tips by the end of the process; as well as locating marks in
order to achieve this process of nanopatterning one layer in the same place
as the layer before.

Then, a 20 nm Cr or Ti was evaporated on top of the resist and the gaps as a


barrier layer and 20 nm Ni was evaporated right after that as a CNT catalyst.
Then the sample was submerged in ethanol to dissolve the PMMA leaving
the catalyst deposited on the right space. It was then covered with a layer of
PECVD

S i3 N 4

layer with a thickness of 200 nm since this kind of layer has

been proved to survive harsh dry and wet etching and front-side deep
reactive ion etching (DRIE).
After that, another pattern is made with a photoresist on top of the
protective layer in order to etch the right part of the protective layer and the
silicon through dry etching. Following the same procedure with the
photoresist the lower part of the sample was wet etched with a KOH
solution where the oxide acted as an etching stop layer.
Later, the photoresists are dissolved and the protective layer was stripped
from the sample. The oxide below the catalyst was stripped as well in order
to make a cantilever.
Finally, CNTs were grown from the defined catalyst spots that were present
on the beams we just had made using plasma enhanced CVD (PECVD).
One of the biggest advantages of this method is that it provides CNT tips
that are directly grown from the silicon cantilevers at the wafer scale, not
manually attached or randomly grown.4 Another one is that, as we have
used e-beam lithography to make the initial holes, both CNT tips location
and diameter are defined by this e-beam process. Finally, their length,
orientation and crystalline quality were controlled by the PECVD. That is
because in PECVD an electric field exists in the plasma and it controls the
orientation of the CNTs (parallel to the electric field). One of the tips
obtained can be seen in the following figure:

Figure ():

But, even though this method had accomplished something that no other
had before (batch production of CNT AFM tips), further study showed that,
after the examination of a large number of tips fabricated under the same
conditions, there was a relatively large variation of the length and a wide
angular distribution of the nanotube tips thus formed5.

As its been explained in section 3, it was possible to create CNT fibrils


starting from a solution of polarisable CNTs and an AC electric field. It is
showed in a following study in 20045 that, with a method based on
dielectrophoresis, it is possible to control and predetermine their length and
orientation.
In this process, a commercial Si AFM probe serves as the working electrode,
whereas the counter electrode is a small metal ring underneath it, with a
layer of the CNT solution. Both SWNT and MWNT were used and can be used
for this kind of experiment.
As shown in the Figure (), the fabrication process consisted on raising the
counter electrode (the ring) slowly until the apex of the AFM probe was
soaked in the solution.

Figure (): Fabrication procedure for the dielectrophoretic method: the ring, working as the
counter electrode and with a layer of the CNT solution, is approached to the AFM tip until the
apex of it is soaked in the solution. Then it is removed leaving a CNT tip.

CNT tips obtained are aligned along the axis of the Si tip due to the
dielectrophoresis force resulting from the interaction between the induce
dipole moments of the CNTs and the electrical field applied between the Si
tip and the ring, that is why all probes seem to have a very low angular
deviation from one to another. The CNT probe is a coagulation of CNT that
end up in a thin fibril. The length of this probe can be controlled by the
distance that the ring was translated under the ac field. This study show a
very uniform result for the CNT probe length.
On the other hand, the diameter of the CNT tip depends on various
experimental parameters, such as the diameter of the initial nanotube
bundle, the concentration of the nanotube suspension, the voltage applied,
and the drawing speed.
5. On the threshold of new methods
5.1. The Langmuir-Blodgett method
Apart from the dielectrophoretic method, other novel methods have been
appearing over time.
One of the methods that has appeared as an upgrade for the conventional
batch CVD method in order to correct the inaccurate orientation of the
nanotubes has been the fabrication method using the Langmuir Blodgett

technique 6; as well as having other advantages over being able to control


the density and thickness as well.
The Langmuir-Blodgett technique is based on the utilisation of a monolayer
assembled on top of a liquid, much like the result of spilling a drop of oil on
a lake. These kinds of layers are called Langmuir layers.
To obtain a SWNT solution for the Langmuir layer, a very specific operation
takes place. According to the study, SWNTs were shortened and
carboxylated by chemical oxidation in a mixture of concentrated sulfuric
and nitric acid under sonication. The resulting filtrated SWNTs were
dispersed into 100ml of aqueous surfactant by 1h of sonic agitation. After
sonication, SWNT solution was centrifuged. The supernatant was then
carefully decanted. This SWNT solution was filtered for removal of
surfactant. The resulting carboxylated SWNTs were then reacted with 4aminothiophenol in the presence of 1-[2-(dimethylanino)propyl]-3ethylcarbodiimide hydrochloride and N-hydroxysuccinimide SWNTs to give
SWNT-SHs. The SWNTs obtained were dissolved in chloroform. 6.
Then, the AFM tip apex is immerged into a water surface and this solution
was spread by pouring minute droplets on the air/water interface. After the
evaporation of the solvent, the hydrophobic SWNTs bundles remained on the
interface and were then compressed by approaching the barriers on the
water surface. Then, through a vertical dipping process shown in Figure 6.1,
the SWNTs were transferred onto the AFM tip apex and then the tip was
dried.

Figure 5.1: a) Experimental setup for this fabrication method. b) Vertical dipping process that
generate the CNT probe.

This is a procedure that presents a vast set of advantages. First of all, it can
be easily done simultaneously for a batch of probes and it is reproducible for
several batches, since the area of the Langmuir film can be as large as
desired. Second, the Langmuir SWNT films are highly aligned so they
provide a proper orientation of the SWNT at the end of the probe. Third, the
film is continuous and homogeneous which leads to a densely packed
coating in the AFM probe which improves mechanical stability.
The results of the study point out a 70% production rate with well-oriented
SWNT probes.
5.2. Electron beam induced Pt deposition method
For this method the probes were fabricated by first attaching the nanotubes
to a nanomanipulator tip with adhesive with the help of an optical
microscope. Later, under the view of a SEM, this nanotube was brought into
contact with a Si probe and fixed to the end of it by deposing platinum
through electron beam induced deposition. It is important to remark that the
nanotube needed to be necessarily in contact with the Si probe for this
method to work; and that the energy of the electron beam is not too high to
avoid a milling effect that would reduce Pt deposition. Then, the
nanomanipulator tip was brought away and the CNT modified as explained
below.
The lateral force constant (

k L=

k L ) of the CNT tip can be expressed as:

r4
L3

Therefore, taking into account that the length of a nanotube is much higher
than its radius, the nanotube probe should be very flexible in the lateral
direction and therefore very likely to bend at small angles.
With the objective of accurately controlling the alignment of the CNT probe,
a focused ion beam (FIB) process was used. By repeated single scanning of
the ion beam imaging, the CNT probe bent towards the FIB beam direction
under every single scan until it was aligned with the FIB beam direction.
A FIB milling process was used too to shorten the CNT probes accurately, by
applying energy on the C-C chemical bonds of the CNT until they had
broken. The carbon atoms were sputtered and the CNT was cut to its desired
length. The effect of both procedures can be seen in the Figure 5.2

Figure 5.2: Effects of FIB alignment and shortening on a misaligned and too long CNT probe

.6.

Conclusion

We have seen some of the most widely known methods for the fabrication of
CNT AFM tips, and its evolution from the very beginning up until more recent
times. It should be remarked that this evolution is not over: This is still an
active field of research that keeps evolving and thus, growing; and that
might be a commercially competitive technique for the fabrication of AFM
tips someday.

Bibliography (in chronological order)


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for Scanning Probe Microscopy: Preparation by a Controlled Process and


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[6]Lee, Jae-Hyeok; Won-Seok Kang; Bung-Sam Choi; Sung-Wook Choi; and
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Note: All figures have been taken from the mentioned articles except for
Figure (), which has been taken from:
Dum, Belle. Scientists Delve Deeper into Carbon Nanotubes. Physics
World, 19 Feb. 2013. Web.
<http://physicsworld.com/cws/article/news/2013/feb/19/scientists-delvedeeper-into-carbon-nanotubes>.