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Contents lists available at ScienceDirect

Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Optical properties of chiral single-walled carbon nanotubes thin films

A. Zawadzkaa,∗, P. Płóciennika, A. Korcalaa, P. Szroederb,∗∗
a
DEPARTMENT of AUTOMATION AND MEASUREMENT Systems, FACULTY of Physics, Astronomy AND INFORMATICS, NICOLAUS Copernicus University, GrudziąDZKA 5, 87-100, Torun,
POLAND
b
Institute of Physics, KAZIMIERZ Wielki University, POWSTAńców Wielkopolskich 2, 85-090, Bydgoszcz, POLAND

ARTICLEINFO ABSTRACT

This work contains experimental results of optical properties for thin films containing Single-Walled Carbon
Keywords:
Single-walled carbon nanotubes Nanotubes. Thin films concerning 0.5, 1 and 2 mg of low dimension chiral (10,6) Single-Walled Carbon
Absorbance Nanotubes dispersed in low concentration aqueous sodium dodecyl sulfate solution (2 mL) were successfully
Raman spectra fabricated by spin-coating technique on transparent substrates at ambient atmosphere. Optical properties of
Photoluminescence these thin films were examined using Transmission, Raman and Photoluminescence Spectroscopies. We find that
Decay time of photoluminescence investigated chiral Single-Walled Carbon Nanotubes show transmission and emission bands not only in infrared
Quantum yield range but also ultraviolet and visible range.

1. Introduction
Nanoscience and nanotechnology provides lots of new opportunities
not only for electronics or photovoltaics, but also for optics and its
practical applications. A growing number of nanomaterials including
organic and organometallic materials [1,2], and carbon allotropes [3,4]
have been shown to possess extremely interesting optical properties. In
particular, carbon allotments discovered in recent decades become one
of the most representative materials of nanotechnology, starting from
carbon nanoparticles (graphite) and ending at fullerenes, carbon na-
notubes (CNTs) or the newest member from this family - recently dis-
covered graphene. Notably, recent studies on carbon nanotubes have
implemented completely new fields of research in materials science,
solid state physics, chemistry, but also optics. Theoretically, CNTs be-
long to the same family as fullerene structures, but their electrical and
optical properties may vary and strongly depend on the structure of the
nanotube.
Carbon nanotubes can be considered as a product of folding gra-
phite layers to carbon cylinders that can have one or more walls. Thus,
single-walled carbon nanotubes (SWCNTs) can be considered as wrap-
ping graphite's layer of the one atom thick, called graphene, into
smooth and uniform cylinder. Most single-walled carbon nanotubes
have a diameter of around 1 nm and can be many million times longer.
The way in which a graphene sheet is wrapped is described by a pair of
indices (chiral indices): n and m. The integer's n and m indicate the
number of unit vectors along two directions in the graphene crystal
lattice that has the honeycomb structure. The pair of n and m indices
determines the chiral vector, chiral angle and diameter of the SWCNT.
The chiral vector C of the graphene sheet can be described as:
⎯⎯→ ⎯⎯→ ⎯⎯ ⎯⎯→
C = n a1 + m a2 , where a1 and a2 are fundamental lattice vectors.
The chiral angle θ and SWCNT diameter can be represented by the
3m
relations: tan θ = 2n + m and d = a n2 + m2π + nm , where
⎯⎯
→ ⎯⎯
→
a = a1 = a2 = 2.46 Å is carbon-carbon bond length [5]. If n= m,
SWCTs are named armchair nanotubes, if m = 0 - zigzag nanotubes and
in any other case they are called chiral (as shown in Fig. 1).
Also conductivity of the SWCNTs shows the dependence on these
two indices. For a given (n, m) nanotube, if n = m, the nanotube
manifests metallic character; if n − m is a multiple of 3 and n ≠ m the
nanotube manifests quasi-metallic character with a very small band
gap. Otherwise the nanotube exhibits conductivity characteristic for
semiconductors [5–9]. The most useful quality to help in understanding
the electronic structures of SWCNTs is the density of states (DOS). The
one-dimensionality of the SWCNT gives rise to 1D sub-bands instead of
one wide electronic energy band in nanotube density of states, as shown
in Fig. 2. Each SWCNT described by indices pair n and m has a unique
set of interband transition energies Eii indicating the energy differences
between the i-th conduction and valence bands. Optically allowed
transitions can only occur between these mirror sub-bands: v1 - c1, v2 -
c2, etc. These transitions (so-called van Hove singularities) are usually
sharp and strong. Dipole-forbidden crossover transitions: v1 – c2, v2 –
c1, etc. are extremely week. Optically allowed transitions are a

∗
Corresponding author.
∗∗
Corresponding author.
E-MAIL ADDRESSES: azawa@fizyka.umk.pl (A. Zawadzka), pawelsz@ukw.edu.pl (P. Szroeder).

https://doi.org/10.1016/j.optmat.2019.109295
Received 31 December 2018; Received in revised form 31 July 2019; Accepted 4 August 2019
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Fig. 1. Scheme of the SWCNT chiral vector.
Fig. 2. Schematic of density of states for a semiconducting SWCNT. Allowed
optical transitions are illustrated as vertical arrows.
characteristic feature of the SWCNTs and responsible for its many dis-
tinguished electronic and optical applications.
The measurement of optical transitions allows, in principle, to de-
termine chiral indices and the bandgap energy of SWCNTs, which is
proportional to the nanotube diameter. Therefore, a huge effort has
been made to measure photoluminescence (PL) of SWCNTs since their
discovery [10–12]. Usually, observation of PL is a result of the isolation
of individual SWCNT that are prevented from assembling with other
semiconducting and metallic carbon nanotubes. Energy transfer be-
tween the semiconducting and metallic carbon nanotubes can occur
and optically-excited carriers are non-radiatively quenched at the me-
tallic carbon nanotubes in the bundled samples [13]. Due to the in-
tensity of the observed PL, most publications concern on experimental
research in the near-infrared (NIR) range of the emission and absorp-
tion spectra [13–15]. The most popular explanation of the PL signal
from semiconducting SWCNTs is recombination of the optically-excited
free electron in the conduction band and free hole in the valence band.
In this one-electron approach without consideration of Coulomb in-
teractions, the resonance features of the optical spectra are attributed to
the sharp electronic states corresponding to the von Hove singularity.
Theoretical calculation for modeling electronic band structure of single-
wall carbon nanotube and their optical transition energies are based on
the tight-binding (TB) model of π-bands of graphene with using the
zone-folding approximation due to its simplicity and some qualitative
agreement with experimental results [16,17]. The tight-binding model
with the nearest-neighbor approximation delivers simple equation to
2jaγ0
calculate optical transitions of the semiconducting SWCNT: Eii = d ,
where A describe carbon-carbon bond length, d – SWCNT diameter, γ0 -
nearest-neighbor hopping parameter and j - an integer. This inverse
proportional trend of transition energies with SWCNT diameter was
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also observed from the Kataura plot [3,18] and Rayleigh scattering
spectroscopy experiments [19].
In 2006 Ando demonstrated theoretically that the Coulomb inter-
action between the electron and hole pair is greatly enhanced in the 1-
nm cylindrical structure and, in fact, that the Coulomb interaction af-
fects the optical spectrum of SWNTs [20]. He showed that the attractive
Coulomb interaction between the optically-excited electron and hole
pair plays an important role in understanding the optically-excited
states in the solid. When the electron and hole are strongly confined in
the 1D system such as the SWNTs with only 1 nm diameter, the at-
tractive Coulomb interaction between the electron and hole is much
enhanced in comparison with 3D bulk materials. The enhanced Cou-
lomb interactions in 1D SWNTs can lead to the formation of tightly
bound electron–hole pairs (excitons) but also strengthen the intensity of
the observed optical von Hove transitions.
Although SWNT has been studied for almost two decades, experi-
mental photoluminescence studies have mainly focused on the study of
isolated nanotubes, their aqueous solutions or solution of purified
SWNTs individually insulated inside surfactant micelles [21–23]. Pho-
toluminescence observed after illumination, regardless of the form of
the investigated material containing SWCNTs, occurred in the infrared
range of the spectrum. The ability of semiconductor material for lu-
minescence and its emission energy depends of course on internal band
structure, but also other external and internal factors. External factors
include above all, the surrounding environment and electric or mag-
netic fields [24–26]. Examples of internal factors include dopants, de-
fects, dislocations but also nearest neighbors interaction and surface
reconstructions (especially for thin films). These factors can empty or
fill existing bands and hence completely change the band structure. As a
result, the energy of photoluminescence emissions can be shifted or its
intensity may be change, causing to strengthen or even total destroy
[27,28]. The case of the SWNTs thin films is particularly interesting,
since for SWNTs all the constituent atoms are on the surface, and they
are therefore all exposed to the surrounding environment and nearest
neighbors interaction.
However, after several years of intensive experimental research,
photoluminescence of the single-walled carbon nanotubes with a dia-
meter of about 1 nm and lower are still poorly tested experimentally.
This is associated with the relatively low intensity of the observed
photoluminescence and its short decay time even in high concentration
inside solutions. Therefore, thin films containing SWCNTs seem to be a
good candidate for this type of research and we decided to fabricated
and investigated them experimentally. Additionally, formation of the
thin film from the solution containing SWCNTs can give long ordered or
disordered nanotubes. The degree of the thin film's ordering depends on
the external conditions applied during the film growth process, in-
cluding electric and magnetic field, gas flow or self-assembly process
[29,30]. On the other hand, thin films with relatively high disordering
exhibit the strongest photoluminescence. Therefore, we decided to in-
vestigate optical properties of the disordered thin films containing
SWCNTs with small diameter. The films were successfully grown on
quartz substrates by using spin-coating techniques. All investigated
films were randomly oriented and their thickness was equal several
hundred nanometers.
2. Experiment
Solutions containing SWCNTs (Nanocyl, 70% purity) were prepared
by using 2 mL deionized water, 0.01 mg sodium dodecyl sulfate (SDS)
and 0.5 mg, 1 mg, 2 mg SWCNTs, respectively. SDS was used to prevent
process of SWCNTs aggregation. Prepared solution was subjected to
ultrasonic bath for 6 h and then immediately after mixing, solutions of
the SWCNTs were used to prepare thin films. The films were grown on
quartz substrate by spin-coating technique in ambient atmosphere. The
preparation of the quartz substrate consisted of four stages of the ty-
pical cleaning procedure. During the first stage, the substrate was
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subjected to ultrasound baths in detergent (15 min) and distilled water

(15 min). Then, in order to improve the surface adhesion and coun-
teract the aggregation of the nanotubes inside the film, quartz sub-
strates were placed in a 30% hydrofluoric acid solution for about 1 min.
In the next stage, substrates were again subjected to an ultrasonic bath
in acetone (15 min) and ethanol (15 min). The last stage of the quartz
substrates preparation was the double cleaning in isopropanol vapors.
The spin-coating process was carried out immediately after the quartz
substrate preparation procedure. A few drops of the solution were ap-
plied to the face surface to cover it completely. Only completely cov-
ered surface allowed to obtain a homogeneous layer. The rotation speed
was the same regardless of solutions concentration and was equal to
2500 rpm. Application of a too high rotation speed led to runoff of the
solution and formation of the inhomogeneous film. The process of film
formation lasted 5 min. We have prepared five samples of SWCNTs thin
films for each concentration. After the deposition all films were sub-
jected to an additional heating process at 50 °C for 2 h in order to re-
move the remaining water residues [31].
Raman scattering spectra of SWNTs were recorded with a Bruker
Senterra Raman microscope. This microscope is designed to deliver
excellent, built-in sensitivity combined with high spectral and imaging
performance. It combines a high throughput Raman spectrometer with
cutting edge optical and electronic components, which provides ex-
cellent detection sensitivity and high spectral resolution without com-
promising confocal spatial resolution. As outstanding sensitivity is the
prerequisite for using low laser power, this microscope allows even the
analysis of sensitive samples such as battery electrodes, carbon nano-
tubes or solar cells. Raman scattering spectra of SWNTs in powder form
were investigated at room temperature in backscattering geometry for
two laser excitation wavelengths (785 nm and 532 nm) and intensity
(10 mW and 20 mW) for.
Transmission spectra were recorder with Lambda 950 Perkin-Elmer
UV/VIS/NIR Spectrometer. This spectrometer is equipped with deu-
terium and tungsten halogen light sources, double holographic grating
monochromators and high-sensitivity photomultiplier, Peltier-con-
trolled InGaAs and PbS detectors, for which allows measurements with
high spectral resolution over a wide spectral range from 175 nm to
3300 nm.
Photoluminescence spectra were recorder with FluoroMax – 4P
Horiba Spectrofluorometer. This spectrofluorometer is equipped with
150 W xenon arc-lamp for excitation, Czerny-Turner monochromators
for excitation and emission and R928P photomultiplier tube for pho-
tocounting detection. This spectrofluorometer allow to measure the
fluorescence or phosphorescence of the solid and liquid sample. While
recording, the emission, the excitation or both wavelengths can be
scanned and variation of the signal with the time, temperature and
polarization can be monitored. The spectrofluorometer system was
controlled by FluoroEssence spectroscopy software.
Fig. 3. Raman scattering spectra of SWNTs for two laser excitation wavelengths
of 785 nm (red color) and 532 nm (green color). Insets on the left hand show
fragments of the Kataura plot corresponding to the excitation energy for me-
tallic (m) and semiconducting (s) nanotubes. Insets on the right hand show
deconvolution of the G band - the circumferential mode (TO). (For interpreta-
tion of the references to color in this figure legend, the reader is referred to the
Web version of this article.)
3.1. RAMAN Spectroscopy
Raman spectroscopy is an important method of study rotating and
oscillating spectra of molecules. The light scattered has different fre-
quencies than the incident light. We observe the shift of lines both to-
wards larger and lower frequencies, and thus larger and smaller en-
ergies can be observed [32–34]. Several features of this spectroscopy
are extremely important. One of them is the possibility of using visible
light to study the Raman spectrum. In our experiment, all Raman
scattering spectra were recorded at room temperature in backscattering
geometry. Measurements were carried out using two laser excitation
wavelengths of 785 nm (1.58 eV) and 532 nm (2.33 eV) having intensity
of, respectively, 10 mW and 20 mW.
Fig. 3 shows the Raman scattering spectra of SWNTs obtained at two
laser excitation wavelengths of 785 nm and 532 nm. The Raman fea-
tures are listed in Table 1. In the low frequency region, we observe the
Raman breathing mode (RBM) band arising from the resonance effects
which occur when the energy of excitation photons fit to the transition
energy between the van Hove singularities in the electron density of
states. Using the simplified formula proposed by Saito et al. [35] linking
the individual tubule diameter, d in nm, with the corresponding posi-
2
tion of the RBM mode, ω RBM in cm−1, d = [51529(ω RBM − 3349.4)]1/2 ,
we find that the diameters of the SWNTs are distributed between 0.9 nm
and 1.7 nm. Insets on the left hand in Fig. 3 show fragments of the
Raman scattering spectra show fragments of the Kataura plot

3. Results and discussion Table 1

Designation and position of the main Raman bands observed at two different
Conducting research on the variety optical properties of carbon energies of the excitation photons.
nanotubes, using SWCNTs is preferable because of its well-defined, Mode ω [cm−1]
simple structure and also simplicity of theoretical and experimental
considerations. Thus, in presented experiment, we use SWCNTs as a 1.58 eV 2.33 eV
form of the thin films and also their water solution to examine all
properties of these unusual structures. SWCNTs nanotubes, by virtue of RBM 146, 200, 227, 262 145, 178, 200, 255
their atomic geometries, should possess very high luminescence M 851
D 1295 1332
quantum yield. Although the possibilities are seemingly infinite, just a −
GM 1536 1516
little is known about the optical properties of these unusual substances, GS− 1561 1549
+
especially when they form a thin film. Raman Spectroscopy, G 1588, 1599 1570, 1583
Transmission, and Photoluminescence measuring techniques were used D′ 1612
2M 1740 1720
to study the optical properties of these species.
iTOLA 1877 1954
2D 2571 2638

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A. ZAWADZKA, et AL.
corresponding to the energy of excitation photons (1.58eV and 2.33eV)
and range of occurrence of RBM. In resonance Raman scattering par-
ticipate both the metallic as the semiconducting nanotubes with a
predominance of the latter. However, due to the selective character of
this process, the RBM band does not provide the full information about
the whole collection of the SWNTs.
The shape of the main Raman G band contains information about
the diameter and metallic/semiconducting electronic type of SWNTs as
well. As we show in the insets on the right hand of Fig. 3, the G band
consists of the GM−and GS peaks which correspond to the circumfer-
ential mode (TO) of metallic and semiconducting SWNTs, respectively,
and two G+ peaks corresponding to the axial mode LO [36]. The posi-
−
tion of the GM and GS in relation to G+depends on the tubules diameter.
d = (C/(ωG+ − ωG −))1/2 , where M 79.5 cm 1⋅nm and
1− ⋅
CS 47.7 cm nm, we find that the diameter of the SWNTs is ranged
=
between 1.1 nm and 1.5 nm and coincide with the estimations derived
from the RBM band. Higher intensity of the GS peak in relation to the
−
GM indicates that semiconducting nanotubes are predominant in the
sample. Besides of the RBM and G mode, we observe the other bands
characteristic to carbon sp2 materials such as the M mode and the
second order 2 M, as well as the disorder induced D band with its
overtones D’ and 2D. The position of that peaks shifts up with energy of
the laser excitation light. Different position of the G+ , G−M and GS we
attribute to the different polarization of the laser incident light of the
length of 532 nm and 785 nm with respect to the nanotube orientation.
3.2. TRANSMISSION spectroscopy
Transmission T(λ) spectra of the SWCNT thin films were in-
vestigated in the spectral range 200–2000 nm. Experimental data for all
investigated thin films are recalculated to absolute values of the
SWCNTs absorbance by elimination transmittance and reflectance of
the quartz substrate covered SDS thin film. Experimentally determined
absorbance spectra are presented in Fig. 4a and shown one wide ab-
sorption band in UV region, located at the wavelength equal to 250 nm.
Absorbance spectra for based solution are present at Fig. 4b. Detailed
analysis of the spectra shows, that intensity of absorbance peak strongly
depend on the concentration of the carbon nanotubes on the substrate's
surface (also the concentration of the based solution). As the con-
centration increases, the intensity of the maximum absorbance also
increases. The absorption of SDS in water solution observed in the
range of 200–1100 nm does not show any absorption maxima and in the
whole range was below the value of 0.1. This clearly indicates that the
observed maxima of absorbance come from thin films of single-walled
carbon nanotubes. An extension of the absorption peak and its shift
towards shorter wavelength was observed for thin films in relation to
Fig. 4. Absorbance spectra of SWNTs for thin films (a) and based solution used for its deposition (b).
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Fig. 5. Kataura plot relates to the nanotube diameter and its bandgap energies.
the solution used for their preparation. Broadening of the absorption
peak indicates the aggregation that occurs during the formation process
of the spin-coated layer.
The effect of the solvent (especially its kind and polarity) on the
location of the absorption maximum is a phenomenon that occurs quite
frequently for many organic and inorganic materials [38,39]. De-
pending on the solvent, it can cause the spectra shift towards longer or
shorter wavelengths. In contrast, the widening of the absorption peak
indicates the aggregation that occurs during the formation process of
the spin-coated layer.
3.3. Photoluminescence MEASUREMENT
Optical properties of carbon nanotubes derive from electron tran-
sitions for one-dimensional structure in the density of state. A typical
feature of one-dimensional structures is that their density of state is not
a continuous function of energy, but descends gradually and then in-
creases in a discontinuous stream. The selection rules show that optical
resonance transitions between van Hove singularities originating from
bands numbered with the same indexes (v1 − c1, v2 − c2, etc.) are al-
lowed. Energies correspond to these transition are named Εii. These
energies are the quantities that characterize each individual nanotube
with indices (n, m) with diameter d. Crossover transitions (c1 − v2,
c2 − v1, etc.) are dipole-forbidden and thus are extremely weak, but
they were possibly observed. Energies between the Van Hove singula-
rities depend on the SWCNT's structure. Thus by varying this structure,
especially the diameter, one can tune the optoelectronic properties of
carbon nanotube.
The first attempt to link and provide the energy Eii values of the
allowed optical transitions of nanotubes (n, m) with a diameter d for
optical spectroscopy was made by Kataura [3]. A typical picture of
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Fig. 6. 3D Photoluminescence spectra for SWCNT thin films: E33 (a) and E22(b) for concentration 2 mg/2 mL, E33 (c) and E22 (d) for concentration 1mg/2 mL, E33 (e)
and E22 (f) for concentration 0.5 mg/2 mL.

Kataura's plot is presented in Fig. 5.
In the semiconductor SWCNT, the van Hove transition with the
lowest energy (E11) corresponds to the absorption or photo-
luminescence directly across the band gap. In the last 10 years, a dy-
namic development of experimental studies using spectrofluorometry to
study transitions of E11 and E22 of a significant number of semi-
conductor SWCNT species has been observed. The first and second van
Hove transient waves were observed for more than one hundred of
SWCNT semiconducting samples and specific structural indicators (n,
m) were assigned to each of these species [15,18,40]. In contrast, ex-
periments with the transitions E33 or higher are very rarely studied.
That is why we decided to experimentally examine transitions E33 and
compare them with E22 for nanotubes with a diameter of about 1 nm. To
explore optical properties a detailed study of photoluminescence was
carried out at room temperature (RT) by using spectrofluorometer
FluroMax 4P Horiba. The temperature dependence of PL in the range

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Fig. 7. PL intensity for SWCNT thin films as a function of concentration for both investigated transitions: E33 (a) and E22 (b).

Fig. 8. PL decay-time for thin film prepared from 2 mg/2 mL concentration: E33 transition (a) and E22 transition (b).

Fig. 9. PL temperature dependence of transition in thin film (concentration 2 mg/2 mL): E33 transition (a) and E22 transition (b) at the excitation wavelength equal to
246 nm.

77–300 K was also examined. 3D Photoluminescence spectra of the
SWCNTs thin film on quartz substrate recorded at RT are shown in
Fig. 6.
These PL spectra were measured in the emission wavelength range
from 350 nm to 900 nm and excitation wavelength range from 230 nm
to 270 nm [41–43]. The highest intensity of the photoluminescence was
observed for the thin films prepared from the solution containing 2 mg/
2 mL SWCNTs – the highest concentration. PL intensities for other
concentrations were significantly lower at RT. The photoluminescence
spectra showed asymmetrical shape regardless the concentration but
for the higher one a typical sharp maxima is started to appear. The
maximum position for both E22 and E33 was independent on the con-
centration of the solution used to prepare the film and was equal to
388 nm and 775 nm, respectively. The intensity of the observed pho-
toluminescence changed significantly. The strongest luminescence was
observed for layers with the highest concentration of nanotubes. With
the decrease of the concentration, the PL intensity also diminishes.
Fig. 7 present PL intensity as a function of SWCNT concentration for
both investigated transitions. A detailed analysis of the presented
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Fig. 10. Temperature dependence of PL Intensity for E33 and E22 lines.
greater than that for the transition E22 at the same excitation wave-
length. This enhancement of the intensity of the photoluminescence for
observed E33 line is the result of UV near-resonant excitation, with the
energy slightly higher than the energy of this line. We have estimated m
and n indexes for the studied nanotubes. In the case of this experiment
these values was equal to (10, 6).
A decay time of photoluminescence for optical transition with the
energy equal to E22 and E33 showed two exponential characters with the
Fig. 11. Temperature dependence of 3D Photoluminescence spectra for SWCNT thin films: E33 300 K (a) and E22 300 K (b), E33 77 K (c) and E22 77 K (d).
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values equal to ca. 1 ns and tens of nanoseconds. Experimental results
are presented in Fig. 8. For comparison, the longer decay time for the
E33 transition corresponds to relaxation forbidden by the selection rules
and is more than three time longer than for E22 transition. These ex-
perimental results may be explain by the existence of trapping center on
the nanotube. The longer decay time τ2 can be assigned to excitons
trapped at defects and impurities, whereas the shorter decay time τ1, is
the effective radiative lifetime. Both decay components have been ob-
served at RT in other experimental studies [44].
In contrast to solution of SWCNTs, solid state samples such as thin
films allow low temperature measurements. This kind of studies in the
low temperature range can permit to gain valuable information about
exciton states structure and existence of a low-lying dark state [45]. In
this study, we were focused on the intermediate temperature range
(77–300 K) and the thermal shift of the E22 and E33 transition. Experi-
mental results for vacuum environment are presented in Fig. 9a–b.
From these figures, a clear spectral shift for both E22 and E33 lines can
be observed. However, this is not simple global shift of the whole
spectrum. Both lines are shifted towards shorter wavelengths (higher
energy), but this shift is not the same. In the case of E33 transition, this
is a continuous shift with temperature increasing. While, maximum of
E22 line practically does not change its position to the temperature of
200 K. Knowledge of the temperature shift in the optical transition al-
lows for accurate measurement of the impact of external deformation of
carbon nanotubes inside thin film [46]. Estimated strain of the SWCNT
when the sample was cooled down to 77 K is of the order of 10−3,
which corresponds to an applied pressure of 109 Pa if one assumes a
Young modulus of 1*1012 Pa for nanotubes.
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Although a limited range of the PL temperature dependence same
other trends can be also noticed. Namely, a significant decrease in PL
intensity with increasing its measurement temperature. Both lines
showed the same tendency, but this change is significantly greater for
E33 transition as shown in Fig. 10. Similar effects have been reported by
Cronin et al. and Karaiskaj et al. for polymer wrapped nanotubes or
frozen suspensions of nanotubes [47,48]. A strong enhancement of
photoluminescence intensity was observed when the excitation wave-
length is from UV range and not so far from resonant with the third Van
Hove singularity, unambiguously confirming the origin of the photo-
luminescence. The observed course of decreasing intensity as a function
of temperature growth is typical for semiconductor materials.
Fig. 11a–d present 3D Photoluminescence spectra of the highest con-
centration SWCNT thin films for both observed transition at the tem-
perature equal to 77 K and 300 K (RT). From these images, in addition
to decreasing the PL intensity and shifting individual emission, one can
also observe a shift of individual excitation towards shorter wave-
lengths. Similar effects have been reported by Lefebvre et al. for pillar-
suspended single-walled carbon nanotubes [49]. They showed that the
atmospheric environment strongly affected the low-temperature lumi-
nescence and PL intensity was quenched at temperatures below ~40 K
for nanotubes in high vacuum, while nanotubes in helium ambient
remain luminescent.
Experimental results of PL and its decay time were used to de-
termine photoluminescence quantum yield. Photoluminescence
quantum yield is an intrinsic property of material which can be ex-
pressed as the ratio of photons emitted to photons absorbed through
photonsem
luminescence, i.e.: QY = photonsabs . The value of PLQY for E 33 transition
was equal to 1.1*10 −3
for 77 K and 5.9*10−4 for RT, and for E22
transition 1.6*10−4 for 77 K and 1.05*10−4 for RT at the UV excitation.
and non-radiative knr relaxation pathways, i.e.: PLQY = k + k∑r k , which
[1]
The PLQY can also be described by the relative rates of the radiative kr
[3] r nr
deactivate the excited state. A calculated value of PLQY indicates that
radiative relaxation is dominant for E22 after excitation at 246 nm. The
value for E33 shows that the same excitation energy causes different the
emission character. Both radiative nonradiative relaxation can be ob-
served and probability of nonradiative relaxation is ten time bigger ten
radiative one. Our results are in a good agreement with those published
by Carlson et al. [50]. Based on all of the above experimental data and
the semi-empirical model proposed by Jamal et al. [51], we estimated
that the observed transitions correspond to SWCNT described by indices
n = 10 and m = 6 with the diameter equal to 1.1 nm.
4. Conclusion
In summary, we have shown that thin films of SWCNTs can be
produced in a simple way using the spin-coating technique.
Concentration of nanotubes inside the film depends on the concentra-
tion of the solution used to its fabrication. Raman spectra together with
absorbance, photoluminescence and its decay time as well as the PLQY
calculations for SWCNT thin films have been presented and provided
many valuable information. We have investigated optical properties of
E22 and E33 transitions for chiral (10,6) SWCNT. In particular, photo-
luminescence and its temperature and decay time dependence has been
analyzed experimentally and theoretically. These concentration- and
temperature-dependent PL studies reveal considerable information
about the optical properties of SWCNTs thin films, such as optical ab-
sorption, emission and band gap energy.
We showed that the temperature dependence of PL spectra can be
considered as the one-photon process. However, both E22 and E33
transition have indicated mixed relaxation at the UV excitation. The
longer component of the decay time have assigned to excitons trapped
at defects and impurities, whereas the shorter component of the decay
time described the effective radiative lifetime of the optical transitions.
The strain of the SWCNT thin film cooled down to 77 K has been
[21]
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estimated as the order of 10−3. The blue shift of whole PL spectra as a
function of the temperature for both investigated lines has been de-
monstrated. PLQY have been experimentally and theoretically studied.
Our experimental results showed that single walled carbon nanotubes
thin films have possessed quite large PLQY compared to other semi-
conductors. So far, these effects have not been considered and experi-
mentally tested by using spectrofluorometry. Low-temperature PL in-
vestigations have shown important features for physics of the SWCNT
thin films and follow-up studies are clearly needed. The high stability of
optical transitions as a function of temperature was very promising
from the point of view of optoelectronic applications.
Declaration of interests
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This research has been financed from the funds of the Polish
National Science Centre (grant no. 2017/25/B/ST7/02124). The films
used in this paper were obtained using Interdisciplinary Centre for
Modern Technologies facilities, NCU, Torun, Poland. The authors wish
to thank the COST Action MP1403 Nanoscale Quantum Optics.
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