CARBON 5 0 ( 2 0 1 2 ) 5 2 1 0 –5 2 1 6

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Raman study of the temperature-dependence of plasma-

induced defect formation rates in carbon nanotubes

Szetsen Lee *, Ya-Chan Liu, Chih-Hsuan Chen

Department of Chemistry and Center for Nano-technology, Chung Yuan Christian University, Jhongli, Taoyuan 32023, Taiwan

A R T I C L E I N F O A B S T R A C T

Article history: Multiwalled carbon nanotubes (MWCNTs) were treated with a low-pressure water plasma,
Received 7 March 2012 and the formation of defects on the MWCNT surface was monitored via the changes in the
Accepted 2 July 2012 Raman D band to G band intensity ratio that occurred with different plasma treatment
Available online 13 July 2012 times and different temperatures. A kinetic model with two competing processes (defect
formation and defect scavenging) was adopted to interpret the observed nonlinear time-
dependent intensity ratio trends. The fitted activation energy (Ea) for the defect formation
process was found to be higher than that of the defect scavenging process. This was
ascribed to the fact that the OH radicals were more effective in reacting with carbon defects
and impurities than with pure CNTs. The Raman-determined Ea’s were also found to be
excitation energy-dependent, with maximum values for red light. Such a unique depen-
dence is characteristic of highly p-conjugated carbon systems.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction oxidation reactions were still carried out at room temperature

Oxidative treatment is widely considered as a key step in the
functionalization of carbon nanotubes (CNTs) for various
applications. Oxygen-containing functional groups formed
on the surface affect the electronic structure and surface
reactivities of CNTs [1]. It is well known that acid treatment
using concentrated HNO3 and H2SO4 can cause the formation
of functional groups, as well as defects, in CNTs [2]; plasma
oxidation using O2 [3] or OH [4] can also produce the same re-
sults as those seen in wet treatment [2]. To date, the plasma
oxidation processes of CNTs has typically been performed
at room temperature. The temperature dependence of the
reaction rate of CNTs has rarely been studied. The relation be-
tween the activation energy (Ea) and the formation of defects
in CNTs [5–11] has been studied to some extent. However, to
date, the Ea information extracted from CNT oxidation reac-
tions has been obtained using the post-reaction annealing,
and not by changing the temperature of the reaction. The
[9–12].
The use of the Raman D band to G band intensity ratio ID/IG
as a criterion for estimating the defect content on CNT sur-
faces has become a common practice. This is based on the
assumption that the G band is a first-order Raman scattering
process, which is unrelated to the D band, a defect-depen-
dent, second-order Raman scattering process [13,14]. In disor-
dered graphite, CNTs, and other sp2 carbon materials, the
relationship between ID/IG and the effective crystalline size
La is well-known. An empirical formula shows that La is inver-
sely proportional to ID/IG [15,16].
In this work, we monitored the temperature-dependent
plasma oxidation rates of multiwalled carbon nanotubes
(MWCNTs), using non-invasive micro-Raman spectroscopy
with excitation energies ranging from 1.58 to 2.54 eV. A reac-
tion model with two competing processes was proposed to
interpret the ID/IG trends observed for the plasma-treated
MWCNTs. The Ea values determined from fits to the tempera-
ture-dependent reaction rate constants were also found to be

* Corresponding author: Fax: +886 32653399.

E-mail address: slee@cycu.edu.tw (S. Lee).
0008-6223/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2012.07.004
 CARBON 5 0 ( 20 1 2 ) 5 2 1 0–52 1 6 5211

excitation energy-dependent, with maximum values occur- dependence on the temperature and excitation energy. For
ring under red light. example, the maximum of the ID/IG curves shifted from
150 min (298 K) to 38 min (873 K) for eL = 1.96 eV, and at
2. Experimental 673 K, the maxima of the ID/IG curves shifted towards longer
times with increasing excitation energy. The averaged stan-
Commercially available MWCNT powder (Functional Materi- dard deviations of the ID/IG values were found to be between
als Division, Mitsui & Co., Ltd, Japan) was purified using a pro- 5% and 9%. We have noticed that there is slight excitation en-
cedure involving HNO3 treatment and H2O2 oxidation, ergy-dependence in averaged standard deviation of the ID/IG
following the procedures reported by Luxembourg et al. [17]. values. The higher the excitation energy (or the shorter the
The purified MWCNT samples were treated in a high temper- wavelength), the higher the deviation (Table 1).
ature quartz discharge tube with a diameter of 25.4 mm A reaction model could qualitatively explain the maxi-
(Fig. 1). The temperature was adjusted from 25 to 600 °C. mum in the ID/IG time-dependence curve. Consider a reaction
The plasma was capacitively coupled, at a radio frequency system with pure CNTs (C), amorphous carbon, oxidation
(RF) of 13.56 MHz. The plasma treatments were carried out debris [18], defective CNTs (A), and OH radicals; A can be cre-
using helium and water. Helium was bubbled through deion- ated from C, or can be oxidized by OH.
ized water at a flow rate of 10 sccm, at a pressure of between
0.05 and 0.2 torrs. Optical emission from the plasma was di- C þ OH ! A k1 ð1Þ
rected to a scanning monochromator (Jobin Yvon, Triax320)
A þ OH ! Products k2 ð2Þ
by an optical fiber. The signal was amplified using a thermal
electrically cooled charge-coupled device (CCD, Jobin Yvon).
where k1 and k2 are rate constants. The corresponding rate
The slit width was fixed at 0.01 mm. The exposure time was
equations can be expressed as
adjusted from 500 ms to 5 s to improve the signal-to-noise ra-
tio. The production of OH radicals was optimized by monitor- d½C
¼ k1 ½OH½C; ½C ¼ ½C0 ek1 ½OHt ð3Þ
ing the emission intensity of OH at 309 nm. dt
Plasma-treated MWCNTs were characterized using a con- d½A
focal Raman microscopy module (Jobin Yvon) with a solid- ¼ k1 ½OH½C  k2 ½OH½A
dt
state GaAlAs diode laser (785 nm), an He–Ne laser ¼ k1 ½OH½C0 ek1 ½OHt  k2 ½A½OH ð4Þ
(632.8 nm), and an Ar ion laser (514.5 nm and 488 nm) to cover
excitation energies eL ranging from 1.58 to 2.54 eV. The CCD where [C]0 is the initial concentration of C. The solutions of
exposure time was varied from 30 to 90 s. The Raman signal the above rate equations yield the time-dependent concentra-
was an average taken from measurements at ten different tions of A.
spots in each sample. The spectral resolution was 1 cm1. Ra-  
k1 ½C0 ek1 ½OHt k1 ½C0
man shifts were calibrated using the silicon reference peak at ½A ¼ þ ½A0  ek2 ½OHt ð5Þ
ðk2  k1 Þ ðk2  k1 Þ
521 cm1. The intensity and linewidth of this peak were also
monitored constantly, to ensure the stability of the laser
where [A]0 is the initial concentration of A. Since A is more
power.
reactive than C when reacting with OH, we can assume that
k2 k1. Thus,
3. Results and discussion
k1
½A  ½C ek1 ½OHt þ ½A0 ek2 ½OHt ð6Þ
k2 0
Fig. 2 shows the temperature- and wavelength-dependence of
the Raman bands for the plasma-treated MWCNTs. The Ra- There is a maximum time tmax corresponding to the max-
man D and G bands for the MWCNTs were all fitted with imum [A].
Lorentzian line profiles. As illustrated in Fig. 3, overlaid 1 k2
graphs of ID/IG versus plasma treatment time showed a tmax ¼ ln ð7Þ
k2 ½OH k1

Fig. 1 – The experimental setup for high temperature plasma treatment of MWCNTs.
5212 CARBON 5 0 ( 2 0 1 2 ) 5 2 1 0 –5 2 1 6

εL = 1.58 eV (298 K) εL = 1.58 eV (873 K)

150 min 25 min

Normalized intensity (a.u.)

Normalized intensity (a.u.)

120 min 20 min

15 min
90 min

10 min
60 min

30 min 5 min

0 min 0 min

1200 1300 1400 1500 1600 1700 1200 1300 1400 1500 1600 1700
-1 -1
Raman shift (cm ) Raman shift (cm )

εL = 1.96 eV (298 K) εL = 1.96 eV (873 K)

150 min 25 min

Normalized intensity (a.u.)

Normalized intensity (a.u.)

120 min 20 min

90 min 15 min

60 min 10 min

30 min 5 min

0 min 0 min

1200 1300 1400 1500 1600 1700 1200 1300 1400 1500 1600 1700
-1 -1
Raman shift (cm ) Raman shift (cm )

εL = 2.41 eV (298 K) εL = 2.41 eV (873 K)

150 min 25 min

Normalized intensity (a.u.)

Normalized intensity (a.u.)

120 min 20 min

90 min 15 min

60 min 10 min

30 min 5 min

0 min 0 min

1200 1300 1400 1500 1600 1700 1200 1300 1400 1500 1600 1700
-1 -1
Raman shift (cm ) Raman shift (cm )

εL = 2.54 eV (298 K) εL = 2.54 eV (873 K)

150 min 25 min

Normalized intensity (a.u.)

Normalized intensity (a.u.)

120 min 20 min

90 min 15 min

60 min 10 min

30 min 5 min

0 min 0 min

1200 1300 1400 1500 1600 1700 1200 1300 1400 1500 1600 1700
-1 -1
Raman shift (cm ) Raman shift (cm )

Fig. 2 – Temperature- and excitation energy-dependence of Raman band profiles of plasma-treated MWCNTs. Excitation
energies are 1.58, 1.96, 2.41, and 2.54 eV (from top to bottom). Left column: 298 K; right column: 873 K.
 CARBON 5 0 ( 20 1 2 ) 5 2 1 0–52 1 6 5213

298 K 298 K

573 K
573 K
ID/IG ratio

ID/IG ratio
673 K 673 K

873 K
873 K
εL = 1.58 eV εL = 1.96 eV
0 50 100 150 200 250 300 350 400 0 40 80 120 160 200 240 280 320
OH plasma treatment time ( min. ) OH plasma treatment time ( min. )

298 K
298 K
573 K 573 K
ID/IG ratio
ID/IG ratio

673 K

673 K

873 K
873 K εL = 2.41 eV εL = 2.54 eV
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400
OH plasma treatment time ( min. ) OH plasma treatment time ( min. )

Fig. 3 – Overlap graphs of ID/IG versus plasma treatment time show dependence on temperature and excitation energy.

½ID =IG  ¼ a0 þ a1 ek1 t þ a2 ek2 t ð8Þ

Table 1 – Averaged standard deviation of the ID/IG ratios.
Excitation Excitation Ave. std. dev.
energy wavelength of ID/IG
1.58 eV 785 nm
1.69 eV 632.8 nm
2.41 eV 514.5 nm
2.54 eV 488 nm
Apparently, two competing processes occur during plasma
treatment. One is a defect formation process (Eq. (1)), and the
other is a defect-scavenging process that is induced by the OH
plasma (Eq. (2)). Because OH is more effective in removing
defective carbon impurities than CNTs, the presence of a
maximum defect concentration (ID/IG) at time tmax results
from competition between the two reactions mentioned
above. Before tmax, the amount of defective carbon increases,
i.e., ID/IG increases. Once the intrinsic defects and impurities
are cleaned up, the only contribution towards the creation
of carbon defects comes from the pure CNTs; this is a slow
(k1) process of production. Therefore, ID/IG decreases after
tmax.
We therefore fit the ID/IG data with a bi-exponential func-
tion (8), according to Eq. (5),
Fig. 4 shows that the fitted rate constants k1 and k2 had a
nonlinear dependence not only on temperature, but also on
excitation energy. k2 showed much larger values and a higher
5.1% sensitivity to temperature than k1. This was consistent with
7.3%
the model proposed above, in which k1 and k2 correspond to
8.0%
defect formation and defect-scavenging processes, respec-
8.6%
tively. OH is more effective in reacting with carbon defects
and impurities than pure CNTs. The Ea values obtained from
the slopes in the Arrhenius plots of ln k1 and ln k2 versus 1/T
showed excitation energy-dependent trends (Fig. 5). Such
trends could be interpreted using double-resonance theory
[19–24]. For example, the D band wavelength-dependent (dis-
persion) effect in the CNTs could be explained by the occur-
rence of disorder-induced double resonance scattering
processes [23,24]. The observed double-resonant modes de-
pend on the energy of the incident excitation light [19]. In dis-
ordered carbon materials, it is known that the sensitivity of
measurements of ID/IG is lower when higher eL is used
[15,25]. In fact, energy/wavelength-dependent Raman spec-
troscopic properties are commonly observed in p-conjugated
carbon materials [4,13,15,16,22,26]. Works on single-walled
carbon nanotubes (SWCNTs) [16] and MWCNTs [4] have also
shown that red light (1.96 eV) has the highest D band intensity,
and produces the highest sensitivity in ID/IG measurements.
5214 CARBON 5 0 ( 2 0 1 2 ) 5 2 1 0 –5 2 1 6

-5
8.0x10 1.96 eV

-5
7.0x10
1.58 eV
-5
6.0x10

-5
5.0x10
2.41 eV

k1 (s )
-5
4.0x10
-1
-5
3.0x10

-5
2.0x10

-5
2.54 eV
1.0x10

0.0
200 300 400 500 600 700 800 900
Temperature (K)

-3
6.0x10 1.58 eV

-3
5.0x10

-3
4.0x10

-3 2.54 eV
k2 (s )

3.0x10
-1

-3
2.0x10 1.96 eV

-3
1.0x10 2.41 eV

0.0
200 300 400 500 600 700 800 900
Temperature (K)

Fig. 4 – The fitted rate constants k1 and k2 show dependence on temperature and excitation energy.

We therefore chose the Ea values obtained with eL = 1.96 eV
(Fig. 6a) as the most valid. Brukh et al. [12] determined Ea val-
ues from the study of the oxidation kinetics of CNTs. Their re-
sults showed that the Ea for the oxidation of MWCNTs is
69.7 kcal/mol (= 291.6 kJ/mol); this is very different from the
values (8.7 kJ/mol for defect formation, and 15.7 kJ/mol for de-
fect scavenging, with eL = 1.96 eV) determined in this work.
Such a discrepancy can be ascribed to the different experi-
mental approaches used. In the study by Brukh et al. [12],
the MWCNT samples were used as received without further
purification, and the oxidation reactions were performed
using an O2/N2 mixture. The measurement of the oxidation
rates were based on the amount of CO2 produced. In our work,
the Ea values were obtained using non-invasive Raman spec-
troscopic technique, and the oxidation reactions were per-
formed using OH plasma. The rates of defect formation/
scavenging were monitored via the spectroscopically deter-
mined ID/IG values.
It is well known that laser power may influence the inten-
sity, position, and linewidth of a peak. Throughout the exper-
iment, we are aware of this issue. The intensity and linewidth
of the D and G peaks were monitored constantly, to ensure
the stability of the laser power and possible heating effect.
As shown in the work by Puech et. al. [27], twofold of source
power increase (from 50 to 100 mW) results in the increase
of the Stoke line intensities of CNTs (D band: 66%, G band:
31%). The corresponding ID/IG ratio increases approximately
27%. Our lasers (source powers: 37.7 mW@785 nm,
22.3 mW@632.8 nm, 7.4 mW@514.5 nm, 22.8 mW@488 nm)
are stable enough not to jump twice in power during each
scan. We believe that the variation of ID/IG ratio due to laser
heating does not prevail over OH plasma treatment and exci-
tation energy-dependence effects in our experiment. From
the linear relation of the ID/IG ratio averaged standard devia-
tion with excitation energy (Table 1), it is clearly seen that la-
ser power-dependence or heating effect may not be
significant in this work.
A recent review paper on defect-induced double-
resonance processes in carbon nanotubes [28] showed that
the product of the ID/IG ratio with the 4th power of laser exci-
tation energy eL was inversely proportional to the crystallite
size La. Thus, the laser excitation energy dependence of the
ID/IG ratios and the Ea values might be eliminated if the ID/IG
ratios were multiplied by e4L. After normalization with e4L , the
 CARBON 5 0 ( 20 1 2 ) 5 2 1 0–52 1 6 5215

-9.0

-9.5

-10.0

-10.5

ln(k1)
-11.0
2.41 eV

-11.5
1.58 eV
-12.0 1.96 eV
2.54 eV
-12.5
0.0010 0.0015 0.0020 0.0025 0.0030 0.0035
-1
1/T (K )

-5

-6

-7
ln(k2)

-8
2.54 eV
1.58 eV
-9

2.41 eV
-10

-11 1.96 eV

0.0010 0.0015 0.0020 0.0025 0.0030 0.0035

-1
1/T (K )

Fig. 5 – Arrhenius plots of ln k1 and ln k2 versus 1/T. The fitted activation energies (Ea) show excitation energy dependence.

linear excitation energy dependence of the ID/IG ratios (disper-
sion) vanished. However, the ID/IG ratios did not converge to
similar values for all of the four excitation energies, as de-
tailed in Ref. [28]. The fitted Ea values with eL-weighted ID/IG
ratios showed a monotonically increasing excitation energy
dependence (Fig. 6b). This implied that the activation energy
of the carbon nanotube oxidation reaction and the crystallite
size were probably not strongly related. In fact, OH radicals
not only react with crystalline CNTs, but also interact with
amorphous carbon, oxidation debris, and defective sites in
CNTs. It is therefore likely that the observed reaction barrier
Ea was the product of contributions from multiple sources.
4. Summary
defect formation processes were found to be higher than
those of the defect scavenging processes. This was consistent
with the fact that OH is more effective in reacting with carbon
defects and impurities than with pure CNTs. The Raman-
determined Ea values were also found to be excitation en-
ergy-dependent, with maximum values observed under red
light. Such behavior can be found in all highly p-conjugated
carbon materials.
Acknowledgements
This work was supported by theNational Science Council of
Taiwan (NSC 98-2113-M-033-002-MY2 and NSC 100-2738-M-
033-001-MY3).

Plasma-induced defect formation on MWCNT surfaces was

monitored via changes in the Raman D band to G band inten-
sity ratio, as treatment time and temperature were varied. A
kinetic model with two competing processes (defect forma-
tion and defect scavenging) was adopted to interpret the
observed nonlinear time-dependent intensity ratio trends
for the plasma-treated MWCNTs. The fitted Ea values of the
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