Optik - International Journal for Light and Electron Optics 229 (2021) 166234

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Optik
journal homepage: www.elsevier.com/locate/ijleo

Original research article

Nitrogen doped carbon nanotubes grafted TiO2 rutile nanofilms:

Promising material for dye sensitized solar cell application
Hamza Belkhanchi a, Younes Ziat a, *, Maryama Hammi b, **, Charaf Laghlimi c, ***,
Abdelaziz Moutcine d, ****, Anas Benyounes e, Fouzia Kzaiber a
a
Laboratory of Engineering and Applied Technologies, Higher School of Technology, Sultan Moulay Slimane University, Beni Mellal, Morocco
b
University of Mohammed V, Laboratory of Materials, Nanotechnologies and Environment, Department of Chemistry, Faculty of Sciences, Avenue
Ibn Batouta, P.O.B. 1014, Rabat, Morocco
c
Applied Chemistry Team, Faculty of Sciences and Techniques of Al Hoceima, Abdelmalek Essaadi University, Al Hoceima, Morocco
d
Molecular Electrochemistry and Inorganic Materials Team, Beni Mellal, Faculty of Science and Technology, Sultan Moulay Slimane University,
Morocco
e
Department of Chemistry, Faculty of Sciences, University of Mohammed V, Rabat, Morocco

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

Keywords: The TiO2 based solar cells are an exciting 3rd class generation photovoltaic, since they hold
Carbon nanotubes promise for the realization of large area devices that can be fabricated by room temperature
N-CNT/TiO2thin films solution processing, that can lead to high photoactive performance. Here, we reported similar
Morphology
efficiencies by focusing our work on obtaining sol-gel thin films belonging to N-CNT/TiO2 system
Optical properties
by dispersing nitrogen doped carbon nanotubes (N-CNTs) powders in titanium tetra-isopropoxide
Electrical properties
Direct band gap using sol gel route. The film samples were evaluated in terms of structure morphology and optical
properties using XRD analysis, atomic force microscopy (AFM) for TiO2, thin film scanning
electron microscopy (SEM) for TiO2 and N-CNT/TiO2 thin films as well as UV–vis absorption
spectroscopic techniques. X-ray diffraction analysis of films produced by the sol gel route and
deposited on ITO glass has shown that they are also amorphous before annealing. However, XRD
spectra showed only the peak of the rutile phase after the high annealing temperatures starting
from 300 ◦ C. The SEM micrographs showed the presence of grains of very small sizes, the grain
size increases with the annealing temperature. The measurements made by AFM revealed that the
thickness and roughness increase with the rise of annealing temperature of the film. 300 ◦ C is the
optimum temperature. This finding was assessed by the experimental investigation of annealing
temperature effect through determination of specific area and pores diameter using BET and BJH
methods respectively.
Moreover, it was confirmed by SEM observations that the grains of N-CNT/TiO2 thin films are
homogeneously dispersed and transmission electron microscopy clearly indicated that TiO2 grains
are adsorbed on N-CNTs. Optical transmittance of N-CNT/TiO2 indicated a decrease with
increasing the incorporated wt% N-CNTs. This behavior is due to charge carriers increase, which
lead to band gap narrowing. The findings concerning the optical gap are assessed by electrical

* Corresponding author.
** Corresponding author.
*** Corresponding author.
**** Corresponding author.
E-mail addresses: ziat.estbm@gmail.com (Y. Ziat), mar.hammi@yahoo.com (M. Hammi), charaf.cac.fbs@gmail.com (C. Laghlimi), abdelaziz.
moutcine@usmba.ac.ma (A. Moutcine).

https://doi.org/10.1016/j.ijleo.2020.166234
Received 19 March 2020; Received in revised form 27 December 2020; Accepted 27 December 2020
Available online 30 December 2020
0030-4026/© 2020 Elsevier GmbH. All rights reserved.
H. Belkhanchi et al. Optik 229 (2021) 166234

measurements. After careful analysis of the results presented in this work, we have deduced that
the mentioned method is found to be simple and more efficient in the calculations of direct band
gap.

1. Introduction

The basic concept of solar cells is to carry out the absorption of photons in an ultra-thin layer in order to cause the formation of
unbalanced electron-hole pairs. The fundamental questions are related to the control of the conditions of generation, transfer and
transport of photo-generated carriers. These conditions will depend on the used materials.
Dye solar cells are made up of three main elements, which are, (i) a semiconductor material with a large optical band gap, with a
large specific surface and responsible for the transport of electrons; (ii) a dye, present in the form of a mono-molecular layer over the
entire surface of the semiconductor, responsible for the absorption of photons; (iii) and an electrolyte containing a redox couple.
Dye-sensitized solar cells (DSSCs) based on nanostructure materials offer very low cost and relatively efficient photovoltaic energy
conversion [1]. There are several important aspects that need to be considered for a photocatalyst as TiO2 in DSSC. Firstly, it must be
able to transfer holes from the sensitizing dye after the dye has injected electrons into the TiO2.
The used routes do not represent any inconvenient to the dye layer on the TiO2 nanocrystallites [2]. by Brian O’Regan and Michael
Gratzel have newly elaborated DSSCs, also called Gratzel cells in 1988, while searching electrodes with higher performance for
electrochemical cells, in the late 1960s, it has been found that illuminated organic dyes can generate electricity at oxide electrodes.
Afterward, many attempts were undertaken in order to find out about photogeneration process which led to many experiments for
electric power generation via the DSSC since 1972. Gratzel et al. have successfully produced the “Gratzel cell,” through TiO2 films [3].
It’s worthy to mention that TiO2 is one of the main third materials generation, indeed the materials used for this generation are
nanomaterials such as cadmium sulfide (CdS), zinc oxides (ZnO), titanium dioxide (TiO2), organic semiconductors (conjugated
polymers, small molecules), and organic dyes.
In our study, we have evidenced that active layer may be composed of N-CNTs and TiO2. Electrons recombination process can be
affecting the conversion efficiency of DSSCs. Since N-CNTs have a special structure and can conduct electrons at room temperature
"without" electrical resistance, the N-CNTs compound can also easily conduct photoelectrons while electrons are generated from TiO2
under light irradiation.
Since their discovery, carbon nanotubes have been the subject of numerous studies in various fields such as composite materials
[4–6], in the batteries of (Li-ion) to increase their performance [7], photovoltaics [8], energy storage [9], or optics [10].Thus, ac­
cording to Web of Science, more than 135,000 articles dealing with carbon nanotubes have been published. Thus, the scope of this
study is to elaborate new N-CNTs/TiO2 thin films which have a potential use as DSSCs.
To do so, within this work we have fixed the elaboration parameters such as annealing temperature and N-CNTs incorporated
amount by in-situ reaction.

2. Synthesis and characterization

The hybrid carbon nanotubes were synthesized by catalytic chemical vapor deposition (CCVD) in a fluidized bed reactor using
ethylene as carbon source and acetonitrile/N2 as carbon/nitrogen source. A typical experiment was carried out initially with ethylene
(600 mL min¡1) for 30 min to produce CNTs. N-CNTs were produced from acetonitrile/N2 for 30 min. The produced carbon nanotubes
were purified by aqueous solution of H2SO4 (50 vol %) under reflux for 3 h.
The coating solution was obtained by dissolving first 2 mL of Titanium isopropoxyde (Ti (OC3H7)4) from Aldrich 98 % 5 mL of
isopropanol, then different weight percents N-CNTs powders ranging from 0.03 wt% to 0.3 wt% of N-CNTs were dispersed inside the
obtained solution. The mixture was stirred at 60 ◦ C for 10 min. Then 5.15 mL of acetic acid was added and new mixture has been stirred
for 15 min. The final mixture was stirred during 2 h after adding 12 mL of methanol to obtain the sol-gel solution. This solution was
spin coated on ordinary ITO glass substrates which were previously in methanol and acetone at different spin speeds (2900, 3200 and
4900 rpm) for 30 s followed by a drying process at 100 ◦ C during 10 min to evaporate the solvent. And finally, the annealing tem­
perature has been elevated subsequently from (100–500 ◦ C). Thus, the mesoporous structure of TiO2 was examined through the surface
area and pores diameter calculations.
Structural and morphological characterizations were determined by X-ray diffraction (XRD), scanning electron microscopy (SEM)
and atomic force microscopy (AFM). UV–vis transmission spectroscopy allowed the study of optical properties. The optical trans­
mission spectra were measured in the visible and near UV range. In addition, the resistivity of the films was measured by the four-point
probe method.

3. Results and discussion

3.1. Annealing temperature effect

Specific area and pores diameter of synthesized TiO2 examined by multi-point N2 gas sorption experiments at 77 K using a
micromeritics ASAP 2010 instrument. The specific surface areas were calculated according to the BET method using sorption data in

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H. Belkhanchi et al. Optik 229 (2021) 166234

the relative pressure range from 0.05 to 0.25 and the pore size distribution was obtained by the BJH method. The evolution of Surface
area and pores diameter versus annealing temperatures are illustrated in Fig. 1.
As one can observe through the Fig. 1, the annealing temperature increases give rise to pores diameter which reaches the maximum
up to 500 ◦ C, in another hand we noticed a systematic decrease of the SBET values. Thus, in order to keep high specific area, the
annealing temperature was limited to 300 ◦ C.

3.2. XRD studies of TiO2 thin films

The samples were investigated by X-RAY diffraction (Diffractometer Pan Alytical X’PERT-PRO) with Cu Kα radiation (λ =1.54060
Å). To elucidate the crystalline phases, we employed a scanning range within 10–35 with 0.04 step recorded every 5 s, the operated X-
ray source were 40 mA and 45KV.
From the Fig. 2, X-ray diffraction analysis of titanium oxide thin films has shown that the latter exhibit an amorphous character
before annealing. After heat treatment at temperatures above 200 ◦ C, we see the appearance of a characteristic peak of thin layers of
titanium oxide at values near 2θ = 31◦ . For the samples having undergone an annealing temperature of 300 ◦ C, the rutile phase is
obtained. The characteristic peak of the found single phase corresponds to the plane (111) of the rutile phase, it shows increased in
terms of intensity by increasing the temperature towards 500 ◦ C, this leads to an increase in grain size.

3.3. Surface characterization SEM

The surface condition of the fabricated samples is crucial in understanding the annealing temperature effects on morphology and
structure. The specimens were observed via a FEI Quanta FEG 450 scanning electron microscope. It should be noted that the mi­
croscope is equipped with a chemical analysis system by energy selection spectrometry (EDX) with accelerating voltage of 20 kV
allowing penetration of the electron beam into the material and leading to the realization of extreme surface chemical analysis.

3.3.1. SEM micrographs of TiO2

The study by scanning electron microscopy (SEM) is presented in Fig. 3 which illustrates the images at high magnification of the
samples before and after annealing at different temperatures ranging from 300 ◦ C to 500 ◦ C. It is shown that the investigated TiO2 films
are composed of small size grains at ambient temperature. The size of these grains increases with the increase of annealing
temperatures.

3.3.2. Atomic force microscopy (AFM) characterization

The surface condition of the films was observed by AFM microscopy. Fig. 4 shows the morphology, in two and three dimensions,
associated with titanium dioxide films annealed at 300 ◦ C and 500 ◦ C. In fact, the roughness (Rms) increases with the annealing

Fig. 1. Specific surface area and pore diameter of TiO2 versus annealing temperature.

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H. Belkhanchi et al. Optik 229 (2021) 166234

Fig. 2. XRD patterns of TiO2 nanofilms deposited and annealed under differents temperatures ranging from room temperature to 500 ◦ C.

Fig. 3. High magnification SEM of titanium dioxide deposited on glass substrate a) without annealing, b) annealing at 300 ◦ C, c) 400 ◦ C and d)
500 ◦ C.

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H. Belkhanchi et al. Optik 229 (2021) 166234

temperature, from 11 nm to the annealed sample at 300 ◦ C, at 55 nm for the sample treated at 500 ◦ C. This leads to an increase in the
thickness of the films, which suggests an increase in the grain size of the titanium dioxide layer. Also, the observation of AFM images
clearly shows an increase in the layer thickness from 200 nm for the sample at an annealing of 300 ◦ C, to a value of 459 nm after
annealing at 500 ◦ C

3.3.3. SEM micrographs of TiO2/N-CNTs

Morphological investigation made by SEM (scanning electron microscopy) analysis. The SEM micrograph of 0.3 wt% N-CNT/TiO2
thin films is given in Fig. 5.
It shows a good homogeneity and the grains consisting of spheres and nanotubes like particles with nanometric sizes. This
observation has evidenced a good dispersion of the particles, also, we note that CNTs are well inserted in the porous layer of TiO2 and
N-CNTs surfaces are covered by the TiO2 particles, which mean that TiO2 is well grafted on CNTs.

3.3.4. Transmission electron microscopy (TEM)

With the view to check the dispersion of N-CNTs and TiO2 nano-powder, transmission electron microscopy was employed to obtain
TEM image of Fig. 6. Note that the conventional TEM characterization was carried out using JEOL-2010 (LaB6 electron gun) with a
Gatan ORIUS CCD camera and a point resolution of 2.34 A.
We deduce from Fig. 6 that the size of TiO2 was about 10 nm and the size of TiO2 was about 10 nm. Also, high resolution TEM
showed that TiO2 nanoparticles were absorbed on the surface of N-CNTs.

Fig. 4. AFM image in 3D and 2D for: a) annealing at 300 ◦ C, b) annealing at 500 ◦ C.

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H. Belkhanchi et al. Optik 229 (2021) 166234

Fig. 5. SEM micrograph of 0.3 wt% N-CNTs/TiO2 thin film.

Fig. 6. Transmission electron microscopy (TEM) image inset EDX spectrum of N-CNTs/TiO2.

3.4. Optical characterization

Spectrophotometry provides information on the optical properties of the sample to be analyzed, it allows the derivation of the gap
energy of the elaborated film, and can lead to the film thickness and optical constants determination. This technique is based to light-
matter dual relationship. Once the studied films absorb ultraviolet or visible light, the absorbed energy lead to excitation of electrons
which jump to higher energy level.
Based on this principle, thin films thickness is extracted from these transmittance data through the following formula [11–13]:
λ1 λ2
d= (1)
2(λ1 n2 − λ2 n1 )

Fig. 7. minima and maxima in transmission spectrum vs wavelength.

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H. Belkhanchi et al. Optik 229 (2021) 166234

Here we consider that since the multiple reflections of light are between the lower surface in contact with the substrate and the free
surface of the film, therefore, there are interference fringes with minima and maxima in transmission spectrum as a function of
wavelength. Hence, λ1 and λ2 wavelengths of two consecutive maxima, TM1 and TM2. As shown in Fig. 7.
Where, n1 and n2 are the refractive index of the layer for the wavelengths λ1 and λ2, the index n1 and n2 are derived from the formula
[14]:

(2)
1 1
n12 = [N + (N 2 − S2 )2 ]2

where S is the refractive index of the substrate and N12 can be calculated by the following equation:

TM − Tm S2 + 1
N = 2S( )+ (3)
TM × Tm 2

3.5. Measurement of transmittance

The fields of spectroscopy are generally distinguished according to wavelength interval in which the measurements are made. We
can distinguish the UV areas, infrared and microwave. In our case, we used a double beam recording spectrophotometer; we could
draw curves representing the variation in the transmittance according to the wavelength in the field of UV–vis spectral range
(200− 800 nm).The transmittance T is defined as the ratio of transmitted light intensity to the incident light intensity, a blank substrate
was used in the reference beam of the spectrophotometer to plot the spectra, a computer connected to this unit reproduces the spectra
representing the transmittance of the thin film, depending on the wavelength incident beam. In these spectra, we distinguish two are
as:
-A domain of wavelengths where the transmittance has series of interference fringes due to multiple reflections in the layers. This
area will enable us to determine the thickness of the layer and its refractive index.
-The second area where the transmittance begins to decrease rapidly will serve for determining the optical absorption edge.
Fig. 8 shows typical spectra of transmittance of N-CNTs/TiO2 layers identified in the wavelength range 200− 800 nm, in N-CNT/
TiO2 films deposited with different of N-CNTs wt % ranging from 0 to 0.3 wt% can be distinguished that the transmittance decreases
with increasing the incorporated wt%.

3.6. Determination of the optical gap Eg

When the wavelengths composing white light are scanned by the spectrophotometer, electromagnetic radiation interacts with
matter. Infrared causes vibrational transitions in molecules while the ultraviolet and the visible cause electronic transitions, the order
of magnitude of the energy radiation caused by these two being that of the binding energies of molecules. This is why the start of
absorption is considered the prohibited bandwidth of a semiconductor. The graphic determination is done according to the principle of
the Tauc tracing method [14–16]:

(αhν)2 = B(hν − Eg ) (4)

Where h: Planck constant, ν: vibration frequency, α: absorption coefficient, Eg: optical gap and B is proportional constant. The pre­
sented curves of (αhv)2 as function of energy represents a linear portion whose intersection with the axis of energy gives the optical gap
Eg. from the transmission spectra we deduced the optical gap of the N-CNTs/TiO2 films.
Fig. 9. exhibits the change of the optical band gap of the elaborated films for different N-CNTs fillers contents. As can be seen the
gap of the neat TiO2 is about 3 eV, in a good agreement with similar energy gap of semiconductors [17], the energy gap value is
reduced due to the increase of the fillers content of the deposited layer. Obviously in the same Fig. 9, we illustrated the determination
of energy gap by the extrapolation method from variation of (αhv)2 versus hv.

3.7. Electric properties of N-CNTs/TiO2 thin films

One of the important electrical properties of the solid thin film surface is the surface resistance, known as sheet resistance defined
by ratio of resistivity to the film thickness, Knowing the values of ρ and thickness of thin films, the sheet resistance can be determined
by the following expression [18–21].
ρ
RS = (5)
d
We have studied the resistive properties of thin deposited on ITO glass substrates. As can be seen in Fig. 10, the measured RS values
show variation with weight percent incorporations of N-CNTs. It is obvious electrical sheet resistance is decreasing systematically with
the increase of charge carriers (Fig. 10).
In DSSC, the N-NTCs are attaching to TiO2 nanoparticles to make charge transport more efficient from the active layer to the
electrodes. The dye injects electrons directly into the TiO2 conduction band and the CNTs act as an “accelerator” of these electrons
towards the electrodes, which would extend their lifespan and consequently improve the conversion efficiency of the cell.

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H. Belkhanchi et al. Optik 229 (2021) 166234

Fig. 8. Plot of transmittance (T) versus wavelength.

Fig. 9. Plot of (αhv)2 versus photon energy hv, for neat TiO2 thin film and N-CNTs/TiO2 thin films.

4. Conclusion

Within this study, we succeeded to elaborate N-CNTs/TiO2 thin films at low temperature and via sol-gel method and deposited on
ITO glass substrates. As Titanium dioxide is known for its applications in the fields of photoactivity and photovoltaics, the choice of
substrates is based on these applications. This is because the glass substrate coated with indium oxide (ITO) is used in solar cells. The
effect of annealing temperature was studied on the structural and optical. Several techniques were used for the characterization of the
samples. Structural and morphological characterizations were determined by X-ray diffraction (XRD), scanning electron microscopy
(SEM) and atomic force microscopy (AFM). UV–vis transmission spectroscopy allowed the study of optical properties. The films were
examined in morphology point of view and the optical properties of the homogeneous films were investigated using UV–vis mea­
surements, the obtained results suggested that the films are of quite high optical quality.
The values of the band gap energy are determined from the transmittance spectra, the determination of energy gap is illustrated by
the extrapolation method from variation of (αhv)2 versus hv.
Also, it was found that the incorporated N-CNTs led to narrowing band gap with increasing N-CNTs content. These results are very
encouraging, thus we have focused our attention on the front of a solar cell element, by carrying out the electrical measurements of the
elaborated thin films. The obtained results corroborated with the optical properties of the elaborated films; these findings suggest that

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H. Belkhanchi et al. Optik 229 (2021) 166234

Fig. 10. Variation of average sheet resistance RS with N-CNT wt%.

these thin films are good candidates for opto-electronics.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.

Acknowledgements

Acknowledgements The authors would like to thank the support of Mr Allal Ziat, Mrs. Fatima El Ouarachi, Mrs. Aïcha Ziat, Mrs.
Saloua Rzaoudi, Mrs Halima Ziat, Mr. Anas Errachid, Mrs. Amina Ziat, Mrs. Khadija Ziat and (Applied Chemistry Team, Faculty of
Sciences and Techniques of Al Hoceima, Abdelmalek Essaadi University, Al Hoceima, Morocco, especially, the professor Jalal Isaad).
Also, we warmly appreciate the discussion of the data with professors:
Mohamed Ghaleb from “Lycée Oulad Youssef, Délégation Béni Mellal, Région Béni Mellal—Khénifra, Maroc”.
Mustapha Rouan from “Lycée Qualifiant Omar Ben Elkhatab, Délégation Fkih Ben Salah, Académie de Béni Mellal—Khnifra, Maroc”.
Hamid El Moutaouakil from “Collège El Qodss, Délégation provinciale Béni Mellal, Délégation régionale Béni Mellal—Khenifra, Maroc”.
Our thanks are extended to Mr. Mohammed Ali Errachid and Ms. Maryem Errachid from “Economy Management, Mohammed 5
University of Rabat, Faculty of Law, Economics and Social Sciences-Souissi, Rabat, Morocco” to accept the language revision. Also, we
are grateful to the professors Fatima Zahra Baghli, Yassine Lakhal, Youssef Ait El Kadi from “the Higher School of Technology, Sultan
Moulay Slimane University, Beni Mellal, Morocco” and Abdelilah Chtaini from “Faculty of Science and Technology, Sultan Moulay
Slimane University, Beni Mellal, Morocco” for their fruitful suggestions.

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