RECENT HIGHLIGHTS IN DEVELOPMENT OF CONDUCTIVITY

PROPERTIES OF CARBON NANOTUBES

Sergio A. Loza-Rosas

University of Puerto Rico, Rio Piedras Campus. Department of chemistry, San Juan PR.

Carbon nanotubes (CNTs) are of the most striking allotropes of carbon today for their
promising mechanical and electrical properties. Since the complete identification of CNTs
by Sumio Iijima in 19911, most of the research had been directed at the study of these
materials.

Single-walled carbon nanotubes (SWCNTs) can be described as the result of rolling a

graphene strip along a vector (n,m), a criterion that defines the radius and the chirality of
which depend on their electrical properties: it has been determined that whenever the value
of (n – m) is a multiple of 3, SWCNT will present a metal conductivity. Any other value of
(n – m) results in a semiconducting SWCNT with a bad gap in the density of states
inversely proportional to the diameter. Following figure 1, the angle formed between
resulting vector from n and m and vector n, called chiral angle (θ), is used to separate
CNTs into different classes (figure 2) with different electrical properties: armchair (n=m,
θ=30º), zig-zag (m=0, n>0, θ=0º). Any other nanotube with an angle 0º<θ<30º is known as
chiral CNT due to different enantiomers that those can have (its mirror images are not
identical). Armchair CNTs are metallic, while chiral and zig-zag CNTs can either
semimetal of semiconductors.2-4
Figure 1. The graphene sheet labeled with the integers (n,m). The diameter, chiral angle and type can be
determined by knowing the integers (n,m). Reproduced from [2], Taylor & Francis (2006).
Figure 2. Examples of the three types of SWCNTs identified by the integers (n,m). Reproduced from [3],
Pearson (2014).

Metallic single-walled carbon nanotubes (M-SWCNT) will present a nonzero density of

states (DOS) at the Fermi level. Semiconducting single-walled carbon nanotubes (S-
SWCNT) will present a band gap at the Fermi level. In any case, the sp2 hybridization of
every carbon atom establishes σ and π systems in the entire network. The energy band of π
system, higher than the σ system band, lies in the region of Fermi level and therefore, the π
system plays a major role in determining the conductivity. As a consequence of the
curvature of SWCNT and size dependence, DOS shows typical van Hove singularities
(vHS) consisting of a singular energy oscillations (spikes) at the DOS (figure 3) M-
SWCNTs shows wider energy gaps between the first vHS than the semiconducting ones
with similar diameters.2,4,5
Figure 3. Differences in vHS gap sizes in M-SWCNTs (dotted line) and S-SWCNTs (shadowed region). It is
important to note that conduction and valence bands remain mixed in M-SWCNTs despite of the gap formed
between vHS.
SWCNTs have potential applications in so-called soft electronic devices of new generation
to replace the rigid silicon-based traditional devices due to the flexibility and promising
electronic properties of SWCNTs when those are coupled with substrate films, generally
polyethylene terephthalate (PET).6 However, these applications are hampered by the
difficulty of the separation of metallic and semiconducting CNTs (M-SWCNT and S-
SWCNT), even more when controlling diameter and the ratio of M-SWCNT/S-SWCNT
produced in synthesis remains a constant issue.7 In addition, low conductivity in CNTs may
occur as a result of defects in the tubes, poorly dispersion upon films and the presence of
high junction resistances between adjacent M-SWCNT and S-SWCNT.8 It is therefore
essential to find alternatives to help overcome these problems and improve the conductivity
of SWCNT films. This review is focused on some of the advances in electrical conductivity
for CNTs.

In theory, doping CNTs network improves the conductivity due to an increase of the
concentration of free carriers and decreased junction resistance between CNTs allowing the
pass of these carriers between S-SWCNT and M-SWCNT9: doping methods can be directed
either during the synthesis of CNT by introduction of heteroatoms in the carbon network or
after synthesis by bombarding ionic species involving chemical adsorption or by insertion
of electro-withdrawing molecules by covalent interactions. In any case, choices are limited
because certain conditions that dopant must present, such as effective electron-withdrawing
with effective extraction of electrons from the valence band (figure 4) and stability under
environmental conditions.7

Figure 4. Density of states (DOS) as a function of energy for (a) semiconducting, (b) doped semiconducting
SWNTs. Reproduced from [10] Accounts of Chemical Research (2013).

As an example of this, AuCl3 shows a good performance as p-type dopant reaching 90% of
reduction of resistance. According to a study, the direction of electron transfer occurring
between the dopant and the CNT depend on the redox potential differences between CNT
and the dopant adsorbed. Au3+ is then such as strong p-type dopant that extracts and it is
reduced by the first and second vHS electrons in the S-SWCNT, and even the first vHS in
the M-SWCNT are removed.11 However, the main drawback is its high hygroscopic effect
leading to the formation of Au clusters in the surface of nanotubes constituting generation
of impurities due to the strong chemisorption of the Au particles to the CNTs. Kim et al12
found that the doping process that increases the conductivity of the CNT film is related to
the chloride anions adsorbed contrary to the general interpretation of CNTs being p-type
doped by means of reduction of Au3+ to Au0 in which electrons were taken to allow this
redox reaction, increasing the hole carriers concentration. To confirm the chloride role in
the doping level, CNT films were annealed using temperatures from 100ºC to 700ºC under
argon environment: data from Table 1 suggests that desorption of Cl- leads to a notable
increase of doped CNT film resistance followed by formation of Au0. Through an annealing
process, in order to reduce structural defects by increasing vibrations, the semiconductor is
treated at high temperatures: in this case, the main consequence of annealing was the
increase of resistance relative to the original AuCl3-doped CNT was expected because of
the removal of the high electronegative electro-withdrawing Cl- at high temperatures
(figure 5).

Figure 5. Cl- associated doping/dedoping mechanism. Reproduced from [12] Acs nano (2011).
Table 1. Change in resistance relative to original undoped pristine sample after 50 days (%) at different
annealing temperature.

Condition 100ºC 200ºC 300ºC 500ºC 700ºC

After -94.1 -70.8 -49.3 -40.33 -30.0
annealing
After 50 -90.9 -64.5 -29.1 -19.9 -9.1
days
difference 3.2 6.3 20.0 20.4 20.9
Reproduced from [12] Acs nano (2011).

The replacement of carbon atoms with impurities on SWCNT walls is a process called
sidewall functionalization or substitutional functionalization: as neighbors of carbon in the
periodic table, boron and nitrogen are the most suitable options for this process. When one
carbon by boron in a hexagon and one carbon by nitrogen in other hexagon in the network
the number of electrons remain constant constituting either p-type and n-type doping. In
addition, their similarities in radii ensures minimum disturbance in the network. As
expected, the replacement of carbon by boron and nitrogen eventually open up the
possibility that gaseous molecules can interact with the walls of CNTs and generate charge
transfer leading to significant changes in conductivity.13

Figure 6. Variation of Fermi energy with boron doping concentration. Reproduced from [14] Carbon. (2007).

It is observed that sidewall functionalization using boron increases the contribution of the π
system at the Fermi level related to the pure CNTs, leading to a high metallic character: that
means that increasing the concentration of boron doping, the Fermi energy will decrease
(figure 6). As a result of the electronic configuration of boron, 1s2 2s2 2p1, doping allows
the decrease of the total number of electrons at the system, explaining the reduction of
Fermi energy.14
Figure 7. Various possible bonding configurations of N associated with SWCNT network (a) pyridine-like
N, (b) pyrrolelike N, (c) substitutional N, (d) nitrile-CN, (e) amine-NH2, (f) single N pyridinic vacancy, (g)
triple N pyridinic vacancy, and (h) interstitial N. Reproduced from [15] Nanotechnology (2009).

Moreover, it has been observed that the nitrogen assumes tow possible hybridizations at the
carbon network: sp3 is the most common leading a 6-fold arrangement (figure 7c), while
sp2 leads to a 6-fold (figure 7a) and 5-fold (figure 7b) arrangement known as pyridine and
pyrrole like structure in SWCNTs. In contrast with the boron doping, nitrogen doping
introduces donor states near to the Fermi level leading to reduction of semiconducting and
achieving a metallic character. Finally, increasing the concentration of nitrogen in the
carbon network leads to the increase of the Fermi energy (figure 8). This is explained by
the increase of the number of electrons in the system due to the electron configuration of
nitrogen, 1s2 2s2 2p3.15
Figure 8. Variation of Fermi energy with N doping concentration. Reproduced from [15] Nanotechnology
(2009).
One of the most useful features for adhering reinforcements to the walls of CNTs lies in the
carbon atoms hybridization: due to the the curvature, significant strain is imparted to sp2
carbon atoms in the network, thereby lowering the energy required to change their
hybridization to sp3 favoring addition reactions. As expected, introduction of a electro-
withdrawing group with will reduce the electron density of the network leading to the
reduce of the Fermi energy, near to the valence band.14

Conclusions
In the pursuit of improving the electronic properties of CNTs films on the growing demand
for soft electronic technology, various methods can be used to increase the conductivity of
these networks taking advantage of the structural properties of CNTs in particular
SWCNTs: certain reactions of addition at sp2 carbon atoms can be carried out by stablishing
covalent bonds between the walls of the tubes and organic molecules even polymers that
containing electron-withdrawing groups and conjugations allow increased conductivity and
decrease of junction resistances with adjacent CNTs.
Adding heteroatoms to the network can mean significant changes in the reactivity of CNTs
and the ability to load change transfers with neighboring molecules in non-covalent
interactions. Moreover, doping processes constitute a large catalog of possibilities where
the best results in increasing conductivity are showed by those electron-withdrawing
dopants that can maintain their capacity and properties under environmental conditions
over time. In any case, the main mission is to obtain a modification of DOS near to the
Fermi level in order to achieve metallic character of the SWCNT, respecting as possible the
π system of the carbon atoms network.

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