Synthesis of nanocrystalline(CdTe:CNT) films for photo device application

Eman M. Nasir, Lamia K. Abbas, Iqbal S. Naji

Department of Physics, College of Science, University of Baghdad, Baghdad, Iraq
Email: eman.nasir@sc.uobaghdad.edu.iq
Abstract
Nanocrystalline (CdTe/CNT) films were produced by the approach of the thermal evaporation at
different ratio of doping and annealing temperatures. It's observed that doping with CNT films have
large effect on the structure and optical characterization. The prepared samples’ structure was
observed with the use of the XRD and AFM; also the optical characterization and optical constants
have been discussed at different ratio of SWCNT. The X-ray diffract grams exhibit the fact that films
that have been obtained are nano-crystal with cubic and hexagonal structure with a 34.15nm grain
size and by increasing CNT ratio to 2wt% the crystallite size decrease to 25.9nm with cubic and
hexagonal structure. The optical constants (i.e. the optical gap, coefficient of absorption, extinction
coefficient, refractive index, and the dielectric constant’s real and imaginary parts) of the
(CdTe/CNT) thin films has been researched as a CNT ratio function in wave-length range of 200–
1000 nm. Analyzing the data of the optical absorption showed that the direct transitions rule is
predominating. It was discovered that the coefficient of absorption, and the coefficient of extinction
(k) is increased while refractive index (n) values and optical band gap decrease with the increase in
CNT ratio at different annealing temperatures,

Keywords: CdTe/CNT, films, AFM, XRD, Optical Characterization.

Introduction
Cadmium telluride (CdTe) can be defined as one of the compound semiconductors, it has an optimal
1.45eV band gap for directly converting light into electricity. Such high optical absorption
coefficient and optimal band gap and optimal edge of optical absorption for the low cost terrestrial
solar energy conversion. Its band gap energy, which is located at the maximal value of the density of
the solar energy incident on the surface of the earth’s results in making Cadmium telluride quite
appropriate for the applications of the solar cells [1]
CdTe film can be prepared by different method, such as vacuum technique, chemical deposition,
liquid phase deposition, epitaxial, etc. from all these techniques, vacuum evaporation is a best
method for the preparation of these materials [2]. Ankita Angreet etal [3] studied the effects of the
temperature of annealing upon the nano-crystalline CdTe thin film grain growth and found that the
phase determined by XRD reveals that the CdTe phase grain size is strongly dependent on the
thickness of the film and has been found to be increasing as the film thickness increases. The thin-
structure of the thin film is important for the electronic applications, however, the high conductivity
of the film is necessary for the applications of the thin-film device. For the purpose of improving
their electrical characteristics, the films must be doped with a proper material [4], In this paper,
CNTs have been used as a doping materials. CNTs were utilized in virtually each one of the device
components for helping the conduction of the charge, improving the flexibility of the electrode and
sometimes as active materials for light absorption. It has been understood as well, that reducing the
NPs sizes will result in dramatically changing those materials’ characteristics [2]. This study aims at
investigating the effects of the doping with the CNT upon the structural. optical and photoconductive
CdTe thin film characteristics.
Experimental:
Cadmium telluride that is doped with CNT at ratio (0, 0.05, 1, 2)wt% films were prepared by
evaporation from high purity CdTe and CNT (99.99%) on glass slides. The deposited film thickness
has been 400nm. All films have been annealed at 100 and 200°C for 1 hours. X ray diffraction
(XRD) technique has been utilized to investigate the structures of films with the use of Shimadzu
6000, with Cu-Kα radiations, operating at 40 kV and 30 mA, the films’ Surface morphology has
1
been examined by AFM (AA3000) .Optical transmission researches were made on the film grown on
glass substrates using UV/VIS spectrophotometer (Optima-3000). The dark current was measured as
a function of applied voltage with the use of the Keithly Digital Electrometer 616 and DC energy
supply, the photo current were done at 75mW/cm2 by using Halogen lamp type philips 120W

Results and discussion:

XRD Studies:
Fig.(1) show X-ray diffraction for CdTe/CNT composite films at different ratio of CNT (0,
0.05, 1, 2)wt% at Ta of 100°C. It appears that these films are polycrystalline of cubic and hexagonal
wurtzite crystalline structure according to JCPDS values. This figure illustrates the crystallization
with strong peak at (111) direction, this means that this plane is suitable for crystal growth, Also this
peak has been much more intense in comparison to the rest and it is often utilized for the high
efficiency solar cells [5]. Peaks of the XRD have been fundamentally observed at 23.72°, 39.28° and
46.44°. Those peaks were corresponding to(111), (220) and (311) cubic structure CdTe planes.
Results have been matching with Data file: cubic 75-2086 for the Cadmium telluride [6]. Also,
peaks of XRD have been observed at 25.32°, 27.42° mainly. These peaks corresponded to the (101),
(002) planes of the hexagonal structure CdTe. With increase CNT ratio the (111) diffraction peak
intensity decreases, representing the reduction in crystalline size of CdTe/CNT films. At 0.2 ratio of
CNT there is a small peaks at (2θ) 25.32° corresponding to the crystal planes 101, indicating that it
has a hexagonal wurtzite crystalline structure[7-9].

Fig(1):The XRD for CdTe/CNT thin films at a variety of the CNT ratios (0, 0.05, 1, 2)wt%.

The observed shifting in the positions of 2θ and the d-spacing values from the ones of standard
reference materials has suggested that the samples that have been prepared were strained. The
decrease in d-spacing and increase in 2theta with increase of CNT ratio are an indication of the fact
that there’s an inhomogeneous tensile stress upon the prepared film crystallites, inducing the strain in
crystallites. Which suggests as well that there are defects like the vacancies, dislocations or
interstitials, then the increasing of doping ratio make distortion in the lattice because the values of
lattice constant vary significantly, Also due to the smaller ionic radius of C (0.16 Å) as compared to the ionic
radius of Cadmium (0.97 Å).
The crystallity size (C.S) size was determined with the use of the Scherrer's equation [7]:

represents wave-length, represents the FWHM and represents Bragg’s angle. The resulted size
of the crystallite as a function of CNT ratio is shown in Fig. 2. The increase of CNT ratio from (0.05,

2
0.1, 0.15, 0.2) wt% decrease the crystallite size and the intensity of the planes. As seen the
CdTe/CNT films crystallite size decreases from 31.5nm to 25.9nm in the case where the doping ratio
increased from 0.05 film to 0.2wt%. Those results suggested that 0.2wt% is an enhanced ratio to
obtain nano crystalline films, micro-strain of the sample (ε) was estimated from:
(2)

Table 2: Structure parameters of CdTe/CNT thin films at different CNT ratio (0, 0.05, 1, 2)wt%.

CNT wt % 2θ(degree) hkl dExp. Å I/Iο

23.72 111c 3.7479 100
0 39.28 220c 3.2918 8
46.44 311c 1.9753 4
23.74 111c 3.7448 100
0.05 39.28 220c 3.2918 5
46.44 311c 1.9753 4
23.74 111c 3.7448 100
1 39.28 220c 3.2918 5
46.44 311c 1.9753 4
23.76 111c 3.7419 100
25.32 101h 3.5146 19
2
39.28 220c 2.2918 11
46.44 311c 1.9753 10

and the density of the dislocation, δ, has been defined as the dislocation length per the unit of volume
of crystal has been evaluated by:

The number of crystallites per the unit of area of CdTe/CNT films (N), was obtained using equation
[7].
(4)
Where, (t) is the CdTe/CNT film thickness.
Fig. (2) Shows the crystallite size, micro-strain, number of crystallites per unit area, and dislocation
density at different ratio of CNT. The crystallite sizes are decreased from 34.15nm to 25.9 nm by
increasing of CNT from 0 to 2 wt%. By increasing CNT ratio the size of the crystallite decreases and
micro-strain, dislocation density and number of the crystallites per the unit of area of the CdTe/CNT
films increases as in Table2. With the decrease in the size of the crystallite the lattice defect increase
results in an increase in micro-strain.the strain; as well as the dislocation density δ; increases with
decreasing the crystallite size[8,9]. These variations may be effect on electrical and optical characteristics of
prepared films.

Fig.(2):The crystalline size, dislocation density, strain and number of crystallites, for CdTe/CNT thin films at different
CNT ratio (0, 0.05, 1, 2)wt% .
Table 2: Calculation of C.S, strain, dislocation density and number of Crystallite of the CdTe/CNT films deposited for (111) plane.
CNT ratio C.S (nm) ε (10-4) δ (A-2x10-5) N (1015/m2)

3
 0 34.15 10.15 0.86 10.05
0.05 31.49 11.01 1.01 12.81
1 31.23 11.11 1.03 13.13
2 25.90 13.38 1.49 23.02

The morphology and size of the grains for the prepared samples was obtained by atomic force
microscopy as in Fig.(3). The grain sizes that have been found by the AFM images have been in
accordance with results that have been obtained using the measurements of the XRD. In these
images, Surface Roughness Average is very small which shows very good smoothness of the surface.
This means that the prepared films are well deposited. The values of Surface topography parameters
like the Surface Roughness Average, RMS roughness, and Ten Point Height for CdTe films at
different CNT ratio were summarized in table. 3

Table 3: Surface topography parameters obtained from AFM analysis for CdTe/CNT thin films at different CNT ratio (0,
0.05, 1, 2)wt%.

CNT ratio 0 0.05 1 2

Grain size(nm) 100 90.24 87.61 85.00
Ra (nm) roughness average 0.341 0.118 0.417 0.418
Rq (nm) root mean square roughness 0.439 0.151 0.519 0.553
Rt (nm) Ten point height 1.65 0.511 1.71 2.43
Rs Surface area ratio 0.00936 0.004 0.0382 0.0141

Fig.(3):AFM graph for CdTe/CNT thin films at different CNT ratio (0, 0.05, 1, 2)wt% .

The optical characteristics of the Cadmium telluride thin films with different CNT ratio (0, 0.05,
1 )wt% atTa of (100, 200)oC of thickness(400)nm were obtained from the U-V spectrum in the
range between (0.2µm and 1.1µm) on glass substrate as in Fig.(4). Transmission of prepared samples

4
has been studied; in general, it's observed that increasing CNT ratio shifts the peak of the spectrum of
transmittance to shorter wave-length at 100oC and to higher wavelength at 200oC compared to the
non-doped films. The peak position films’ shift can result from impurity by decreasing the grain size
and this is in agreement with our result of XRD and AFM. Also the spectra of absorpttance have
been depicted in Fig.( 5) it has been obvious that its behaviour is the opposite to the transmittance
spectrum behaviour [8].
100 100
200C
100C
pure
pure
80 80
0.05wt%
0.05wt%

1wt%
1wt%
60 60

T
T

40 40

20 20

0 0
200 400 600 800 1000 200 400 600 800 1000

Wavelength(nm) Wavelength(nm)

Fig4:The transmittance spectrum of CdTe thin films with different CNT ratio (0, 0.05, 1)wt% at Ta(100 and 200)oC .

It has been noticed that the transmittance and reflection is decreased, whereas absorbance is
increased with increasing CNT ratio and Ta as shown in Table.1 and this is due to decreases the
grain size by increasing the impurity[9-11], and slightly, the shift of the absorption edge to smaller
wave-length (higher photon energy) at Ta 100 oC and to higher wavelength at 200oC.

5
 1.2
1.2
pure
pure
0.05wt%
1
1 0.05wt%
1wt%
1wt%
0.8
0.8

A
A

0.6 0.6

0.4 0.4

0.2 0.2

0 0
200 400 600 800 1000 200 400 600 800 1000

Wavelength(nm) Wavelength(nm)

Fig.( 3)The absorpttance spectrum of CdTe thin films with different CNT ratio and Ta.
Table.1 The value of optical constant at 0.666 μm
Ta(oC) CNT% T A R α(cm- Eg(eV)
1)
x104
100 pure 0.143 0.719 0.137 4.141 1.76
0.05 0.202 0.626 0.171 3.608 1.68
1 0.175 0.667 0.156 3.846 1.6
200 pure 0.175 0.668 0.156 3.847 1.66
0.05 0.119 0.759 0.121 4.374 1.6
1 0.11 0.776 0.113 4.469 1.5
Fig.( 4) shows the coefficient of absorption (α ) of CdTe thin films with various ratio of CNT
annealing temperatures (100 and 200)oC .From these figures, α increases with the increase in
the temperatures of annealing for every prepared sample as can be seen from Table1 and that results
from decreasing energy gap value with doping and annealing temperatures. The values of α varies as
in Table.2

6
 7 7

100C pure 200C

pure
6 6
0.05wt
0.05wt%
%
1wt%
5 5

a(cm)-1x104
4
a(cm) -1x104

3 3

2 2

1 1

0 0
200 400 600 800 1000 200 700

Wavelength(nm) Wavelength(nm)

Fig4 The absorption coefficient of CdTe thin films with different CNT ratio and Ta.

To know the optical transition type, (αhν)1/2, (αhν)1/3, (αhν)3/2, (αhν)2 have been examined vs.
the hν and it has been discovered that the last equation has resulted in a linear dependence,
describing the permitted direct transitions. From Figure.(5) the values energy gap have been
specified from the plotting of the Tauc equation and taking the linear portion’s extrapolation.

7
 180
180
100C
200C
160
pure 160
pure

140 0.05
140 0.05
1%

(αhυ.eV/cm)^2x10^8
120 1%
120
(αhυ.eV/cm) 2x10^8

100
100

80 80

60 60

40 40

20 20

0 0
1 1.5 2 2.5 1 1.5 2 2.5
hv(eV)
hv(eV)
2
Fig.(5)(αhν) as a function of photon energy for CdTe thin films with different CNT ratio (0, 0.05, 1)wt% at
Ta(100 and 200)oC
where (α ≥104cm-1) of (αhν)2 as an hν curve function to α=0. The value of the direct energy gap has
been discovered as can be seen from Table1, which almost agrees with other literature works [9].
The optical energy gap value decreases with the increase in the CNT ratio and annealing temperature
as shown in Table(1) and Fig.( 5), and this is due to the decreases of the grain size and the increases
the ratio of CNT impurity this is turn decreased the value of Eg. This result agrees approximately
with other result [10,11]
The materials’ optical behavior is used in general, for the determination of its optical
constants, such as refractive index (n). Table (2) show the variations of the value of the refractive
index CdTe thin films with different CNT ratio (0, 0.05, 1)wt% and Ta(100 and 200)oC. It is sould be
noted that n is decreased with the increase in the CNT ratio and Ta. such behavior results from the
decrease in reflection that the refractive index is dependent upon.
The extinction coefficient (k) behavior is almost similar to the corresponding coefficient of
absorption Table(2) at different CNT ratio and Ta, from this Table, k increases with increasing CNT
ratio and Ta. This results from the same reason that has been mentioned earlier in the coefficient of
absorption Table2 illustrates the variations of the real dielectric constant (ε1) and the imaginary
dielectric constant (ε2) with different CNT ratio and Ta. The behaviour of ε1 is similar to that of the
refractive index, due to the smaller k2 value in comparison to n2, whereas ε2 is mostly dependent
upon k values, associated with absorption coefficient variations. It has been discovered that ε1 is
decreased, and ε2 is increased with the increases in Ta and the ratio of the CNT.

Table2. The values of optical constant at 0.666μm

Ta(oC) CNT% k n ε1 ε2
100 pure 0.219 2.151 4.579 0.945
0.05 0.191 2.387 5.663 0.913
1 0.203 2.288 5.197 0.933
200 pure 0.204 2.288 5.195 0.933
0.05 0.232 2.031 4.073 0.942
1 0.237 1.98 3.865 0.938

8
The properties of the current-voltage (I-V) of a device at the dark conditions have been illustrated in
Fig. 6(a). The value of the dark current is increased with the increase in the bias of the voltage. From
that figure also, dark current is increased with the increase in the CNT ratio duo to free charge
carriers which found by the increases of impurity in the prepared films. The photo-current is
assessed with the use of the light source as can be seen from in Fig6(b). It shows clearly that the
CdTe:CNT films have photo-conductive property and photo-current is increased with the increase in
the illumination, even though photo-current isn’t that high in comparison with the dark current.
None-the-less, the flow of the current via the device can be limited by the effects of the space charge
in the thickness of the film or the carrier tunneling over a barrier not related with films[12]. It’s easy
perceiving that photo-absorption process generates the electron-hole pairs in the CdTe cluster with
quite low efficiency. Voltage current (I-V ) exhibits an increase in the linearity, indicating the fact
that there is continuous voltage increase, Therefore, space-charge –limited current (SCLC)
dominates the carrier transport process[12-14].
The voltage increases the current. It has been shown clearly that Cadmium telluride films have
photo-conductive characteristic [12]. The photo-current not so high in comparison to the dark
current.
9 10
pure 1% at dark
8 9
0.5wt% 1% at light
8
7 1wt%
7
6
Current (x10-6 Amp)

Current (x10-6 Amp)

6
5
5
4
4
3
3
2
2

1 1

0 0
0 10 20 30 0 10 20 30
Voltage (Volt) Voltage (Volt)

Conclusions:
CdTe films with thickness (400) nm on glass at different ratio of CNT and annealing temperature
(100,200)oC have been prepared
The XRD tests of these films at different ratio of CNT showed that the structure is poly-crystalline
with cubic and hexagonal structure (FCC) with predominately (111) orientation. From x- ray and
AFM measurement, the grain size increases with increasing of CNT ratio. From optical properties
calculation, it's found that the increasing in ratio of CNT shifts the transmittance spectrum peak
compared with un doped films. The coefficient of absorption increases with the increase of the ratio
of CNT for every sample, the optical energy gap are direct transitions and decreases with the
increasing CNT rati within the range 1.76-1.5eV .The dielectric constant (1) and refractive index (n)
decreases with CNT ratio, while the coefficient of extinction (k), and dielectric constant (2)

9
increased with the increase in the CNT ratio. The prepared films have photo-current response which
may be utilized for the photo devices applications

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