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Article history:
Received 23 March 2015
Received in revised form
30 July 2015
Accepted 31 July 2015
Available online 7 August 2015
Here, we investigate the thickness of single-walled (SWCNT) and multi-walled carbon nanotube
(MWCNT) random network lms by angle-resolved X-ray photoemission spectroscopy. Furthermore, we
estimate the absorption coefcient of carbon nanotube (CNT) lms through the LamberteBeer law, by
measuring lm optical spectra. Moreover, the knowledge of the absorption coefcient provides an easier,
reliable, and faster method of investigation for generic CNT lm thickness. In addition, the absorption
coefcient leads to the information of the absorption length for SWCNT and MWCNT lms, which is a
physical quantity of fundamental interest for optoelectronic applications, such as light emitting diodes,
photovoltaics, and in general light absorbers.
2015 Elsevier Ltd. All rights reserved.
1. Introduction
The thickness of carbon nanotube (CNT) lms is a fundamental
quantity in order to understand their optical and electronic properties. However, measurements of the lm thickness are often
fraught with large and undesirable uncertainties, owing to the thin
lm high degree of roughness or in general to its complex
morphology [1]. In particular, this is notably for non-vertically
aligned CNT lms. Therefore, local scanning probe microscopy
such as atomic force microscopy (AFM) and even non-local, such as
scanning electron microscopy (SEM) cannot provide a reliable
estimation of the CNT lm thickness, because they usually are very
sensitive to the CNT lm surface roughness [2].
A closely related quantity to the CNT lm thickness is its absorption or extinction coefcient. The latter is of paramount
importance to characterize the optical and optoelectronic properties of CNT lms [3]. So far, the estimation of CNT absorption
29
our method, not only may be very useful and effective for the
estimation of generic CNT lm thickness, but also can be used to
tailor in a controlled fashion the thickness of CNT lms, simply on
the basis of the volume of the CNT dispersion.
2. Experimental details
2.1. Fabrication of CNT lms
Highly pure CoMoCAT SWCNT powder (SigmaeAldrich, assay
>90%, diameter: 0.7e0.9 nm) and CCVD MWCNT powder (Nanocyl,
NC3100, assay >90%, diameter: 5e9 nm) were dispersed with
several concentrations in aqueous solution with 2% w/v sodiumdodecil-sulfate (SigmaeAldrich, assay >98.5%) anionic surfactant.
In addition, to better disperse the suspension, CNTs were tipultrasonicated (Branson S250A, 200 W, 20% power, 20 KHz) in an
ice-bath for an hour and the unbundled supernatant was collected
by pipette. The result was a well-dispersed suspension which is
stable for several months. Carbon nanotube lms were fabricated
by a vacuum-ltration process of aliquot volumes of the dispersion
cast on mixed cellulose ester lters (Pall GN6, 1 in diameter,
0.45 mm pore diameter). Subsequently, rinsing in water and in a
mixture of ethanol, methanol, and water (15:15:70) to remove as
much surfactant as possible was performed. Samples were made
depositing by the dry-transfer printing method [1,2] two cut parts
of the same CNT lm; one on Carlo Erba soda-lime glass slides for
optical absorption measurements, and the other part on HF etched
silicon (100) wafers for AR-XPS experiments.
2.2. Optical spectroscopy and electron microscopy
Optical spectroscopy (Perkin-Elmer Lambda 19 UV/Vis/NIR) was
performed to characterize the absorption coefcient of CNT lms.
We measured the transmittance T(l) I/I0 spectra of CNT lms for
wavelengths l in the UV/Vis/NIR range, where I and I0 are the intensities of light transmitted by the CNT lm deposited on a glass
substrate and by a reference bare glass substrate, respectively. We
then calculated the corresponding absorbance A(l) spectra by the
known equation A(l) log10T(l). Scanning electron microscopy
micrographs were acquired with Zeiss Leo Supra 35 eld emission
scanning electron microscope (FEG-SEM).
2.3. AR-XPS measurements and modeling
The CNT lm thickness was measured by AR-XPS measurements
of CNT lms deposited on silicon wafers, as previously reported [8].
The AR-XPS data were collected with a SCIENTA R3000 analyzer,
operating in transmission mode and working with an acceptance
angle of 30 . Based on the electrostatic lens setting of the analyser
and the X-ray source spot on the target, the sampled area is about
3 3 mm2. The AlKa line (hn 1486.6 eV, resolution 0.85 eV) of a
non-monochromatized dual-anode PsP X-ray source was
employed, running at a power of about 110 W. The base pressure in
the sample analysis chamber was z1010 mbar. With the sample
holder clips being coated with gold, the binding energy
(Eb 83.96 eV) [31] of the Au 4f7/2 peak was taken as a reference.
The measurement of the CNT layer thickness is based on the
attenuation of the core level intensity signal from the Si substrate
for different CNT coverages. This measurement can be carried out at
different extents, from the attenuation determined by inelastic
scatting events alone, to more sophisticated models that also
include elastic scattering processes and the use of the depth distribution function (DDF). In the present case, the CNT layer thickness was estimated by collecting the C 1s and Si 2p core level
intensities at different take-off angles q (Fig. 1).
Zdt
IEk ; q K
FEk ; q; zdz;
(1)
where K is a normalization constant, which includes the photoionization cross section, the atomic density of the species, and
analyzer-dependent parameters; F(Ek,q,z) is the generic escape
probability or DDF of an electron generated at a depth z with a
kinetic energy Ek at an angle q with respect to the surface normal.
According to the LamberteBeer law, the DDF function is usually
approximated with a Poisson distribution [33] F exp(z/Lcosq)
where L is the inelastic mean free path of the photoelectrons [37].
Such an approximation leads to a simple analytical expression for
the peak areas, which is dened as a straight line motion [35].
However, this formulation may result in an overestimation of the
top layer thickness, especially for thin overlayers. Here, we used
DDF calculations [33], in order to account for both inelastic and
elastic electronic scattering processes in the so-called transport
approximation [34]. Furthermore, the photoemission asymmetry
parameters are taken into account for each core level and calculations of electronic trajectories are computed to predict the AR-XPS
peak areas in the CNT-Si interface, since an analytic DDF formulation [35] cannot be written for a generic multilayer sample.
3. Results and discussion
3.1. Measure of the CNT lm thickness
Several samples were realized by ltering different volume aliquots of the same CNT aqueous dispersion. The obtained lms are
random networks of SWCNTs or MWCNTs, as evident from SEM
micrographs in Fig. 2aed. From grazing incidence SEM images in
30
Fig. 2c,d, it can be observed that the high roughness due to the
complex microstructure of CNT lms makes the estimation of the
lm thickness a hard task. Therefore, in order to overcome this
issue, we performed AR-XPS measurements on CNT lms, which
provides an estimation of the average lm thickness probed by
electrons. The overall trend of the angular dependence of the
photoemission spectra is detectable in Fig. 3a, which shows the ARXPS data of C 1s and Si 2p core levels collected for a MWCNT-Si
interface at different take-off angles q. These data have been
collected as survey spectra with a pass energy of the analyzer set at
100 eV and averaging over 50 scan for each spectrum. As can be
observed, both the C 1s and Si 2p intensities change with the takeoff angle. In particular, as q increases, the measure becomes more
surface sensitive, therefore the signal intensity from the Si substrate decreases, while the intensity of the C signal increases. For a
detailed data analysis and modeling, high resolution and low-noise
AR-XPS spectra have subsequently been collected by setting the
analyzer pass energy at 50 eV and averaging the signal over 1300
scans for each spectrum. In order to evaluate the CNT lm average
thickness, we used the model described in Section 2.3, where the
intensity of each AR-XPS peak is strongly dependent on the thickness t of the layer itself and on the thickness d of all the other layers
above (see equation (1)). This means that the AR-XPS intensity of
any layer under the CNT lm is connected to the thickness of the
CNT lm itself. In this framework, it is fundamental to proceed with
a suitable normalization (involving both sides of equation (1)) of
the AR-XPS peak intensity, to properly account for instrumental
factors which are independent on the take-off angle and on the
sample itself. Therefore, the Si 2p spectra have been normalized to
the C 1s intensity. The sequence of Si 2p AR-XPS spectra, normalized to the C 1s peak area and collected at different take-off angles,
is shown in Fig. 3b. Following Ref. [8] the Si 2p were tted by three
or four Voigt peaks accounting for bulk Si (one peak), SiO2 (one
peak), and a non-stoichiometric silicon oxide (SiOx) layer which
develops at the CNT-Si interface, as the samples are stored in air. In
particular, one and two peaks were used for the SiOx contribution in
MWCNT and SWCNT respectively, to account for the different
extent of the oxidation processes at these two CNT-Si interfaces.
The binding energies of the Si related peaks are: 103.4 eV (SiO2),
100.1 eV (SiOx), 99.5 eV (Si). The origin of the peaks are discussed in
Fig. 2. Scanning electron micrographs of SWCNT (a,c) and MWCNT (b,d) lms at different magnications 10,000 (c,d) and 200,000 (a,b). Carbon nanotube lms appear as dense
and porous (dark holes) random networks (a,b). In the image taken at grazing incidence (c,d) (z90 respect with the plane normal), it is possible to observe micro-structures
consisting in self-assembly ripples made of SWCNTs. Conversely, MWCNTs just aligned in the vertical direction. Dark areas is the underneath glass substrate.
31
Table 1
Results of AR-XPS and spectrophotometry measurements.
Sample
SWCNT01
SWCNT02
SWCNT03
MWCNT01
MWCNT02
MWCNT03
29.2
31.4
36.1
22.2
28.6
35.4
0.8
0.9
2.2
0.8
1.2
5.3
Al alt:
(2)
Fig. 3. (a) Angle-resolved X-ray photoemission survey scans of the C 1s and Si 2p core
level regions for the sample MWCNT01 deposited on Si at different take-off angles
q 0 ,10 ,20 ,30 ,40 ,50 . (b) High resolution Si 2p AR-XPS dataset. All the Si 2p peaks
were normalized to the C 1s and tted with three Voigt curves ascribed to SiO2 (peak 1
in red), SiOx (peak 2 in gray) and bulk Si (peak 3 in blue). (c) SiO2 (red dots), SiOx (gray
dots), and Si (blue dots) peak areas as functions of take-off angles, normalized to C 1s
area (green dots) that was set to 1.0. Solid lines represent tting results. Please note
that data points for SiOx and SiO2 at 20 are superimposed because they have the same
value. (For interpretation of the references to color in this gure legend, the reader is
referred to the web version of this article.)
32
Fig. 4. (a) Absorption spectra of SWCNT and MWCNT lms for different aliquot volumes. (b) Estimation of SWCNT (blue dots) and MWCNT (red squares) absorption coefcients
through the LamberteBeer law. (c) Absorption coefcients of SWCNT (blue solid line) and MWCNT (red solid line) lms. Colored regions represent the rst S11, the second S22, and
the third S33 optical transition ranges for semiconducting SWCNT chirality, and the rst M11 range for metallic SWCNT chirality. The MWCNT lm has no signicant absorption peaks
but the p-p* surface plasmon polariton at z253 nm (5.1 eV), while for the SWCNT lm it is centered at z243 nm (4.9 eV). (d) Absorption lengths of SWCNT (blue solid line) and
MWCNT (red solid line). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
4. Conclusion
In summary, we fabricated SWCNT and MWCNT thin lms by
vacuum-ltration of aqueous dispersions. Such lms were deposited on substrates by dry-transfer printing at room temperature.
Furthermore, SEM images revealed the complex nature of CNT
random networks, which makes the estimation of their lm
thickness very difcult. Therefore, in order to obtain the CNT lm
thickness we performed AR-XPS measurements. Then, we discussed the optical spectra of CNT lms, once estimating their absorption coefcients with the LamberteBeer law and the obtained
AR-XPS lm thickness. Also, we provided an estimation of the CNT
Fig. 6. Thickness of SWCNT (blue dots) and MWCNT (red squares) lms as a function of
the dispersion aliquot volume. (For interpretation of the references to color in this
gure legend, the reader is referred to the web version of this article.)
33
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