Journal of Alloys and Compounds 604 (2014) 253–259

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Structural and optical characterization of CdTe quantum dots thin films

M.M. El-Nahass a, G.M. Youssef b, Sohaila Z. Noby c,⇑
a
Physics Department, Faculty of Education, Ain Shams University, Roxy, Cairo 11757, Egypt
b
Physics Department, Faculty of Science, Ain Shams University, Abbassia, Cairo 11566, Egypt
c
Physics Department, National Research Centre, Dokki, Cairo 12622, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: Cadmium telluride quantum dots (CdTe QDs) have been synthesized using hot-injection chemical
Received 24 February 2014 technique. The CdTe QDs thin films were deposited onto optical flat fused quartz substrates using thermal
Received in revised form 20 March 2014 evaporation technique. The CdTe QDs powder and the as deposited films were characterized using X-ray
Accepted 21 March 2014
diffraction and high resolution transmission electron microscope (HRTEM). The X-ray analysis shows that
Available online 29 March 2014
both CdTe QDs powder and the as deposited films crystallize in cubic zinc-blende type structure with lat-
tice parameter 6.46 Å and 6.45 Å, respectively. The X-ray calculation shows that the average crystallite
Keywords:
size of the as deposited CdTe QDs films varied from 1.1 nm for the powder to 2.3 nm for the thin film.
Quantum dots
Nanoparticles
The HRTEM examination of the as deposited films shows that the average particle size vary from
Optical constant 2.5 nm for the powder to 2.7 nm for the thin film. For the as deposited films, the dependence of (ahm)2
CdTe thin films on the incident photon energy indicates that the optical transitions within the film are allowed direct
Single oscillator model with energies observed at Eg1 ffi 2 eV and Eg2 ffi 2:3 eV which attributed to quantum confinement effect.
The optical band gap increases from 1.5 eV for microstructure CdTe to 2 eV for nanostructure quantum
dots which corresponding to wavelength(620 nm) so it is a great benefit to use CdTe quantum dots as
solar harvesting devices application in solar spectrum region (400–800 nm). Urbach energy is calculated
and found to be 360 meV which is higher than microstructure CdTe. The refractive index and refractive
index dispersion of the as deposited CdTe QDs film has been calculated from transmission and reflection
spectra. It has been found that the refractive index is reduced from (2.66) for microstructure CdTe to be
(1.7) for CdTe quantum dots. The variation of the refractive index at normal dispersion is well described
by Wemple–DiDomenico single oscillator model. The dielectric constant at infinite frequency e1 and the
ratio of free carriers’ concentration to the effective mass (N/m⁄) are calculated and discussed. Finally, the
non linear optical parameters are calculated using some empirical relation.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction place of microstructure CdTe to fabricate many optoelectronic

Among II–VI semiconductor binary systems, microstructure
CdTe is of technological importance due to its ideal band gap and
high absorption coefficient. CdTe material is used in photovoltaic
applications, photorefractive and magneto-optical properties and
is extensively used in the fabrication of solar cells, nuclear
radiation detectors and electro-optical modulators, etc. [1]. On
the other hand, nanoparticle based thin films have a great potential
applications for a new generation of semiconductor devices which
including solar cells, transistor, optoelectronic devices,
photochemical and nonlinear optical materials [2–4]. Therefore,
colloidal CdTe quantum dots (CdTe QDs) thin films which maintain
quantum size effects from the constituent particles are used in
⇑ Corresponding author. Tel.: +201284331120.
E-mail address: scientist_sohaila@hotmail.com (S.Z. Noby).
devices. Despite the fact that the performance of the CdTe QDs
optoelectronic devices may still in the developing stage the poten-
tial advantage are evident. Apart from the increasing band gap of
the semiconductor CdTe QDs, quantum confinement can provide
additional benefits such as efficient multiple exciton generation
which enabling a short path toward inexpensive yet efficient pho-
tovoltaic devices [5–7]. In addition, technically, the use of CdTe
QDs nanoparticles for thin film deposition might offer significant
advantages over conventional microstructure material deposition
such as higher surface diffusivities and reduction of melting tem-
perature of nanoparticles and also lower processing temperature
[8]. Additionally, due to the small particle diameter of the starting
nanoparticles used an improved packing during deposition is oc-
curred which leads to smoother and denser deposited films.
In this article, we report the synthesis of CdTe QDs powder using
hot injection chemical technique followed by deposition of CdTe

http://dx.doi.org/10.1016/j.jallcom.2014.03.104
0925-8388/Ó 2014 Elsevier B.V. All rights reserved.
254 M.M. El-Nahass et al. / Journal of Alloys and Compounds 604 (2014) 253–259
QDs thin film. The structural of both CdTe QDs powder and as
deposited film are determined. Additionally, the spectral reflection
and transmission of the as deposited film were measured from
which the optical properties of CdTe QDs nanocrystalline thin film
were extracted. Moreover, the absorption coefficient and optical
energy gap of the CdTe QDs thin film were obtained. Furthermore,
the room temperature refractive index and refractive index disper-
sion of CdTe QDs thin film are calculated. Also, a connection between
the variation of refractive index dispersion and microstructure
parameters of the as deposited CdTe QDs film has been established
through single oscillator dispersion model that directly relates the
dispersion energy parameter Ed to the variation of coordination
number and other physical parameters of the investigated film.
Finally, the nonlinear optical parameters of the as deposited CdTe
QDs thin film were calculated by using some empirical relations.
2. Experimental details
2.1. Syntheses
The CdTe QDs powder was prepared in the crystal growth facility exist in Nano-
Tech. Lab., Egypt. The CdTe quantum dots were synthesized via the hot-injection
chemical technique [9], where the pioneering work of such preparation method
was proposed and published by Murray et al. in 1993 [10]. In the present work,
the average size of the CdTe QDs powder was intentionally synthesized to be
around 2.5 nm. Such value of the average size gives strong confinement of the elec-
tron and holes with the dots [11].
2.1. Preparation of CdTe QD’s thin films
CdTe quantum dot thin films were prepared by thermal evaporation technique
using high vacuum coating unit type Edward E306A England. The quartz substrates
used for deposition, of type slide microscope, were cleaned with great care in ultra-
sonic hot bath, distilled water and ultra-grade pure alcohol. Prior to evaporation
started, the CdTe QDs powder was loaded in molybdenum boat and the coating unit
was left for a while to reach a pressure as low as 2  104 Pa. The conditions of
deposition were completely controlled through the rate of evaporation which was
adjusted at 0.2 nm/s. During deposition process the substrate temperature was kept
at room temperature. To ensure good homogeneity of the deposited films, the sub-
strates were rotated during deposition process at low speed (2 rpm). Finally, the
thickness of the deposited films were continuously monitored using quartz crystal
thickness monitor of type Edward FTM4 and is found to be 191 nm. The thickness of
the deposited films was checked independently using Tolansky’s method with error
estimated around 2.4% [12]. These experiential details can be found in the recently
published articles [13–15]. CdTe QDs thin film is fabricated from the starting QDs
nanoparticles using thermal deposition technique in which bulk-like polycrystal-
line film is obtained. In the process of thermal deposition, organic ligands are re-
moved and the nanoparticles are fused into each other to form clusters and
ultimately grains, which changes the properties of the deposited materials [16].
Understanding the transition from quantum confined QDs nanoparticles to
polycrystalline film is crucial to realize properties of the electronic devices with
nanoparticles based like solar cells [17].
At room temperature, the crystal structure of the quantum dots powder and
as-deposited films were identified using X-ray powder diffraction (XRD) of model
Philips X’’-Pert with Ni-filtered Cu Ka – radiation. The XRD patterns were measured
in step-scan modes; in a 2h range between 10° up to 80° with step size of 0.03° and
step time of 0.6 s. Pure Si  99.9999% has been used as calibrated standard sample.
A high resolution transmission electron microscope (HRTEM) of model Joel JEM
-2100 with acceleration voltage of 200 kV and transmission electron microscope
(TEM) of model JEOL JEM-1230 with acceleration voltage 80 kV were used to inves-
tigate the surface morphology and to measure the particle size of CdTe QDs depos-
ited films.
In wide wavelength rang, the optical characterization of the as-deposited films
were measured by measuring the transmittance and reflectance as a function of
wavelength. The measurements were performed using double beam UV–Vis–NIR
spectrophotometer of model Jasco (V-570) in spectral range 200–2500 nm. The
transmittance spectrum was collected at normal incidence while the reflectance
spectrum was recorded at 6° off the normal to the sample surface.
3. Results and discussions
3.1. Structural characterization
The room temperature XRD pattern of the CdTe QDs powder
and the as deposited film are depicted in Fig. 1a and b. For CdTe
QDs powder, the diffraction peaks measured at 2h° equal to
23.73°, 39.67° and 46.11° are reflected from the crystallographic
planes (1 1 1), (2 2 0) and (3 1 1), respectively. These peaks are
almost the same as the one indexed on the basis of the cubic
zinc-blende ZnS type structure of card No. (JCPDS No. 75-2086)
without detecting any secondary phases for CdTe compound.
Furthermore, the XRD pattern for the as deposited CdTe QDs film
shows the same diffraction peaks as for the powder with preferred
crystallographic orientations along (1 1 1) plane. The lattice param-
eter (a) of the cubic unit cell of CdTe QDs powder thin film was cal-
culated using the known relation for the cubic system
2 2 2 2
dhkl ¼ a2 =ðh þ k þ l Þ. For and CdTe QDs powder and as deposited
film, the lattice constant a, as shown in Table 1, was calculated for
the three peaks (1 1 1), (2 2 0) and (3 1 1). The average values of the
lattice constant, a, of the powder and as deposited film were 6.46 Å
and 6.45 Å, respectively. These average lattices constant agree very
well with the reported results for CdTe compound [18–20]. The
crystallite size of CdTe QDs is calculated using Debye–Scherrer’s
formula [21]:
0:89k
D¼ ð1Þ
b cosðhÞ
where k is the wavelength of X-ray source (k = 1.5416 Å), b is the
full width at half maximum of the maximum peak (FWHM) and h
is the Bragg’s angle. It is worth to mention that in case of small crys-
tallites D = 3L/4, where L is the diameter of spherical nano particles
[22]. The nanosize nature of the as deposited film is clearly mani-
fested in the large full width at half maximum (FWHM) of the dif-
fraction peak (1 1 1) compared with the same peak in the powder
form. The calculation shows that the average crystallite size of the
as deposited CdTe QDs film decreases from 2.3 nm for the powder
to 1.1 nm for the as deposited films. This result suggests growing
small crystallites on larger ones [23] which leads to large surface
scattering so large broadening in diffraction peaks occur. The strain
introduced as a result of the difference between lattice constant of
the as-deposited films and the substrate can be evaluated from the
following relation:
D
e¼ ð2Þ
4 tanðhÞ
For cubic zinc-blende structure of CdTe QDs film, the disloca-
tion density has also been calculated using the following relation
[24]:
1
d¼ ð3Þ
D2
a (111) Powder
(220)
(311)
Intensity (a.u)
(111) Thin film
b
(220) (311)
10 20 30 40 50 60
o
(2θ ) degree
Fig. 1. XRD patterns of a-powder and b-thin film CdTe quantum dots.
 M.M. El-Nahass et al. / Journal of Alloys and Compounds 604 (2014) 253–259 255

Table 1
XRD data of the CdTe QD powder and as deposited thin film.

(h k l) Powder Thin film

2h° d (Å) a 2h° d (Å) a
(Å) (Å)
(1 1 1) 23.727 3.74694 6.56 23.99 3.70646 6.42
(2 2 0) 39.67 2.27025 6.42 39.76 2.2652 6.41
(3 1 1) 46.111 1.9326 6.52 46.17 1.9646 6.52
Average lattice 6.46 6.45
constant

For powder, the calculated values of e and d are 1.69  102

lin m and 1.2717  1017 lin/m2, respectively. On the other hand,
2

for thin film the calculated values of e and d are 4.5  102 lin2 m
and 1.74  1018 lin/m2, respectively. It is clear that as the particle
size decreases, the micro-strain and dislocation density increase.
These results are similar to those reported by Lalitha et al. for CdTe
material [25].
The surface morphology of the synthesized powder and the
deposited film was examined using HRTEM technique. For exam-
ple, we depict in Fig. 2(a and b) the TEM photographs of the CdTe
QDs powder as well as the as deposited nanocrystalline thin film.
The image depicted in Fig. 2a illustrate that the synthesized pow-
der is of nanostructure QDs structure with spherical asymmetry
(elongation along some direction). For the as deposited films
Fig. 2b illustrates high resolution image of the preferred orienta-
tion along (1 1 1). The high-resolution TEM image shown in
Fig. 2b indicates that the lattice spacing of the CdTe QDs films
equal to 0.4 nm, such value corresponds to the distance between
the (1 1 1) family of planes of the cubic zinc blende structure of
microstructure CdTe (where the lattice constant a = 6.45 Å) with
relative error around 6% [26]. In addition, Fig. 3 indicates that the
deposited film has a tightly packed grains and smooth fine surface.
As it clear in Fig. 2c some particles size was found to be around
1 nm in thin film form and this confirm the results obtained from
XRD. The average particle size evaluated from TEM images was
found to be 2.5 nm for powder and 2.7 nm for thin film. The
particle size identified from TEM is slightly larger than the one
determined from XRD technique. The TEM is held to give the more
accurate measure while XRD suffers from systematic errors
[27,28]. The structure and morphology of the CdTe QDs films inves-
tigated in the present work agree very well with the reported
results for other CdTe QDs nanoparticle and films prepared by
other physical and chemical techniques [18,20,29,30].

3.2. Absorption coefficient and optical energy gap of CdTe QDs thin film

The spectral distribution of reflectance R(k) (dotted line) and

transmittance T(k) (continuous line) of the as deposited CdTe
QDs of thickness 191 nm is depicted in Fig. 3. For a film deposited
onto optical flat fused quartz substrate, the measurements of R(k)
and T(k) nanocrystalline CdTe QDs are measured in the wavelength
range 200–2500 nm. The substrate absorption is corrected by
introducing an uncoated cleaned quartz substrate of the same type
Fig. 2. HRTEM images of CdTe quantum dots: (a) powder, (b) powder’s lattice
as the one on which CdTe QDs is deposited in the reference beam of parameter (d-space) and (c) TEM of CdTe quantum dots thin film.
the spectrophotometer. As shown in Fig. 3, the transmittance spec-
trum shows a highly optical transparency (T(k)  90%) from
2500 nm down to 1500 nm. In the spectral range 1500 nm down In the strong absorption region, the optical absorption coeffi-
to 500 nm, a steady decrease in transmittance is observed (absorp- cient a of the investigated film is evaluated from the experimental
tion process within the QDs film starts to take place). After that, the data of transmittance T and reflectance R using the following rela-
transmittance starts to decrease steeply until it approaches zero at tion [31]:
the fundamental absorption band edge of the CdTe QDs film. This 2 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi3
2 4 2 2
sharp edge corresponds to electron excitation from the valance 1 4ð1  RÞ þ ð1  RÞ þ 4R T 5
band to conduction band and interrelated to the nature and value a ¼ ln ð4Þ
d 2T
of the optical band gap within the electron confined in CdTe QDs.
256
1.0
Film thickness = 191nm
Intensity (R & T) %
0.8
0.6
0.4
0.2
0.0
500 1000
Wavelength (nm)
Fig. 3. The transmittance TðkÞ and reflectance RðkÞ spectra of CdTe QDs thin film.
where d is the film thickness, T and R are the transmittance and
reflectance of the investigated film, respectively.
The optical energy band gap, Eg, of the investigated CdTe QD’s
film can be determined from optical measurements by fitting the
data to the Tauc’s relation of the form [32]:
p
ðahmÞ ¼ a ðhm  Eg Þ
where a is constant equal to a ¼ ðe2 =nch me Þð2mr Þ which de-
pends on effective mass ðme Þ, reduced mass (mr) of charge carries,
the refractive index of the material (n), the Plank’s constant h and
the speed of light c. hm is the incident photon energy and the p is
an exponent that depends on the type of the band transitions in-
volved; e.g. p = 1/2 or 3/2 for allowed direct interband transitions
and forbidden direct interband transitions, respectively and p = 2
or 3 for allowed indirect interband transitions and forbidden indi-
rect interband transitions, respectively. The intercept of the linear
extrapolated fit to the experimental data of the relation (ahm)2
verses incident photon energy (hm) gives the value of the direct opti-
cal band gap while the extrapolation of the linear part of the plot
(ahm)1/2 verses incident photon energy (hm) gives the value of the
indirect optical band gap of the investigated film.
For the as-deposited CdTe QDs thin film, Fig. 4 shows the vari-
ation of (ahm)2 as a function of the incident photon energy (hm). The
presented results show a direct electronic transition across the
optical band gap of the deposited film. The extrapolation of the lin-
ear part of the (ahm)2 curve to the photon energy axis would give
the optical band gap within the CdTe QDs film. The results depicted
in Fig. 4 show two allowed direct transitions observed at Eg1 ffi 2 eV
and Eg2 ffi 2:3 eV, respectively where Eg1 is the lowest optical band
gap, Eg2 is higher transition energy which can be explained based
on quantum confinement effect. This effect transfers the continu-
ous distribution of density of states to discrete levels in conduction
4x10 9
3x10 9
(α hν )2 (e.V/cm)2
2x10 9
1x10 9
0 0
1.0 1.5
Photon energy (e.V)
Fig. 4. The variation of (aht)2 with the photon energy hm.
M.M. El-Nahass et al. / Journal of Alloys and Compounds 604 (2014) 253–259
band and valance band and also the distance between levels in-
creases [33] so a lot of transition can be occurs between this levels.
T The binary system CdTe is a direct band gap semiconductor mate-
R rial with room temperature absorption edge observed at
Eg = 1.475 eV (841 nm) [34]. As the CdTe material transformed
into quantum structure like QDs a blue shift of the energy gap is
observed [35]. Such blue shift depends on the size of the synthe-
sized QDs can be clarified according effective mass approximation
developed by Brus [36–38]:
!  
p2 h2 1:8e2
EgðQDsÞ ðRÞ ffi EgðBulkÞ þ  ð6Þ
2l R
 2 4pee R
1500 2000 2500
where the first term of Eq. (6) is the energy of the microstructure
CdTe material, the second term is the electron–hole quantization
within the dots and third term represents the coulomb attraction
between electron and hole embedded within the dots [36]. The val-
ues of the parameters presented in Eq. (6) are: reduced mass of the
electron–hole pair l⁄ = memh/(me + mh) (me = 0.11mo, mh = 0.35mo
for microstructure CdTe) where mo is the electron rest mass [39],
Eg(Bulk) is the energy gap of the microstructure CdTe Eg(Bulk) = 1.475
eV [34], e (7.1), eo are the dielectric constant of the investigated
material (CdTe) and permittivity of vacuum, respectively [34], and
ð5Þ R is the average radius of the QD’s  1.35 nm. Substituting with
2 1:5 the aforementioned parameters into Eq. (6) and using Eg(QDs) = 2 eV
we found that the particle radius is 2.6 nm.
For the direct band gap material like CdTe, indirect transition
can be occurred due to the transitions between various allowed
levels in the valance and conduction band. As illustrated in Fig. 5,
indirect transition is observed with energy namely at 1.0545 eV
with a phonon assisted of energy 33 meV. Similar observation
are reported by several researches [40,41], so we assume that there
is a shallow levels below the conduction band edge with ener-
gy  0.95 eV which can be calculated as (Eg-direct–Eg-indirect) as ob-
served by Mathew and Enriquez [42].
Previously, the absorption process above the band gap is con-
sidered; however, absorption just below the optical band gap can
be characterized by disorders which induce band tail in the absorp-
tion coefficient a. The absorption coefficient of the band tail states
changes exponentially as a function of photon energy hm of the
form [43]:
 
hm
a ¼ a exp ð7Þ
Eu
where a is a constant and Eu is the band tail energy or Urbach en-
ergy, which measures the degree of disorder within the investigated
film material. This simply means a large Urbach energy corresponds
to a high level of disorder inside film material. For the CdTe QDs
thin film, Fig. 6 shows the dependence of ln(a) versus photon
200
(α hν )1/2 (e.V/cm)1/2
100
2.0 2.5 3.0 1.0 1.5 2.0 2.5 3.0
Photon energy (e.V)
1l2
Fig. 5. Indicates indirect transition ðahtÞ versus photon energy hm.
 M.M. El-Nahass et al. / Journal of Alloys and Compounds 604 (2014) 253–259 257

energy. The value of Eu is determined directly from slope of the 2.0 0.07
straight line and it is found to be around 360 meV. Such value is

extinction coefficient (k)

higher than the value for microstructure CdTe material 29 meV 0.06

Refractive index (n)

[17]. The large Urbach energy for CdTe QDs is more likely attributed
to the variation of the particle size (disorder in particle size) since
the particle size vary from 1 nm up to 2.7 nm (strong quantum
confinement QDs). These results agree very well with the reported
results for the CdTe and CdSe nanoparticle published previously
[44,45].
3.3. Refractive index dispersion of CdTe QD’s thin film
The value of optical constants, refractive index (n) and extinc-
tion coefficient (k), has been calculated using the theory of light re-
flected from and transmitted through thin film layer deposited on
thick substrate according to the following relations [46]:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ð1 þ RÞ 4R 2 (EoEd)1, and the intercept, Eo/Ed of the straight line shown in
n¼ þ k
ð1  RÞ ð1  RÞ2
where
ak
k¼
4p
Fig. 7 shows the calculated optical constants of the CdTe QDs
thin film. As shown in Fig. 7, the refractive index exhibits anoma-
lous dispersion behavior in wavelength range 350–830 nm and
normal dispersion in wavelength range greater than 830 nm. In
the same figure, the variation of absorption index k as a function
of wavelength is illustrated.
3.4. Single oscillator parameters of CdTe QDs thin film
The variation of the refractive index dispersion of the investi-
gated CdTe QDs film can be understand and analyzed in terms of
the single effective-oscillator model proposed by the Wemple–
DiDomenico (WDD) [47]. The model suggests that the refractive
index n of the investigated film is simply related to the electronic
structure of the film material by the following equation:
E Ed
n2 ðhtÞ  1 ¼ 2
ð10Þ
½E2  ðhtÞ 
where E is the single oscillator energy of electronic transition and
Ed is the dispersion energy which is related to the average oscillator
strength of the optical transitions [48]. As shown in Fig. 8, the val-
ues of E and Ed can be extracted from the graphical representation
of (n2  1)1 versus (ht)2 and fitting the experimental data to
straight line identified by Eq. (10). The oscillator parameters Eo
and Ed shown in Eq. (10) are directly identified from the slope,
1.9
0.05
1.8 0.04
0.03
1.7
0.02
1.6
0.01
1.5 0.00
500 1000
Wavelength (nm)
Fig. 7. The variation of n and k with the wavelength for CdTe QDs thin film.
ð8Þ
Fig. 8. The calculated values of E and Ed are given in Table 2 to-
gether with reported values of microstructure CdTe by (W–D) [48].
At zero photon energy, the refractive index n1 (n at hm ? 0 or
k ? 1) is related to the infinite dielectric constant e(1) by
ð9Þ e(1) = n2(1), is deduced from the dispersion relation by extrapo-
lating the linear part to intersect with the vertical axis at zero pho-
ton energy. The calculated value of n(1) for CdTe QDs thin film is
shown in Table 2 and it is smaller than its value in bulk CdTe thin
film (n = 2.66 [49]). We suggest there are three reasons for lower-
ing of refractive index in nanostructure CdTe thin film. First, its
nano-confined dimension which is smaller than the incident wave-
length so we can deduce that Rayleigh scattering occurs [50] inside
the thin film of nanostructure so according to that the refractive in-
dex decreases. Second reason, the refractive index of a semicon-
ductor decreases with the increasing in the energy band gap Eg
according to various empirical rules and expressions that relate n
to Eg [51,52]. Third reason is the increase of surface-to-volume ra-
tio of atoms in nanomaterial so a lot of scattering occurs [33]. So
we can deduce that refractive index in nano CdTe thin films re-
duced so it is a great benefit in solar cells application where the
reflection also reduced so absorption increases.
The importance of WDD model is that it relates the dispersion
energy parameter Ed to other physical parameters of the film mate-
rial investigated through the following empirical relation [47,53]:
Ed ¼ bNc Z a Ne ð11Þ
where b is a two-valued constant with either ionic value
(bi = 0.26 ± 0.03 eV) or covalent value (bc = 0.37 ± 0.04 eV), Nc is
the effective coordination number (CN) the cation nearest neighbor
to anion, Za is the formal chemical valency of the anion, Ne is he
effective number of valence electrons per anion. For CdTe

9.0 0.44

8.5
-1

0.42
(n -1)
ln (α)

8.0 0.40

7.5 0.38
1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
2 2
Photon energy (eV) E (e.V)
2 1 2
Fig. 6. The relation between ln(a) and photon energy hm. Fig. 8. The relation between ðn  1Þ and ðhtÞ for CdTe QDs thin film.
258 M.M. El-Nahass et al. / Journal of Alloys and Compounds 604 (2014) 253–259

Table 2 (eL). In addition, the higher value of the ratio (N/m⁄) may be attrib-
Optical parameters of the as deposited CdTe QD’s thin film. uted to the small electron effective mass within the dots which is a
Optical parameters E (eV) Ed (eV) e(1) n1 Nc (eL) direct consequence of the alteration of the band structure and
Nanostructure 4.535 10.752 3.37 1.8 1.7 3.656
density of states of the CdTe QDs compared to the microstructure
Microstructure CdTe [56].
Ref. [51] 7.1 2.66 –
Ref. [49] 4.13 25.7 4
3.5. Non-linear optical constant

The non-linear optical response of a material to an incident

semiconductor of zinc blende structure, the value of b equal to 0.4 optical field can be expressed by the following relation [57]:
and Ne = 8 [47], therefore, from the extracted value of Ed we can de-
duce the value of Nc for CdTe QDs thin film. This value is given in pðtÞ ¼ vð1Þ EðtÞ þ vð2Þ E2 ðtÞ þ v3 E3 ðtÞ þ . . . ð13Þ
Table 2 together with value of Nc for microstructure CdTe according (1) (2)
where v is the linear susceptibility, v is the second order sus-
to WDD model. The value of Nc for CdTe QDs thin film is smaller ceptibility which describes processes such as second harmonic gen-
than its corresponding value for microstructure CdTe. The decrease eration and v(3) is third order susceptibility (non-linear optical
of, Nc, for CdTe QDs thin film leads to a decrease in the interaction susceptibility) which describes third harmonic generation and
between the structural layers. This result agree with the fact that intensity dependent-refractive index. Several semi-empirical for-
electrons in quantum dots are treated as artificial molecules [54] mulas were suggested for calculation of the term v(3) or n2 nonlin-
and may be also due to dangling bonds in quantum dots materials ear refractive index among these formulas the one suggested by
represented due to capping material which in our case tri-octyl- Boling et al., which relates n2 to linear refractive index [58]. In addi-
phosphine (TOP). tion, Petkov and Ewen discussed in more detail the integration of
To gain more deep understanding of the physical properties of Boling’s formula with WDD single oscillator model for linear refrac-
the material under investigation, it is appropriate to know more tive index dispersion n and they obtained a relation for n2 that re-
information about the lattice dielectric constant (eL) and carrier lates to some structural parameters of the investigated film [59].
concentration (N). According to Spitzer et al. model, the real com- Additionally, Tichy et al. used Miller’s generalized rule in com-
ponent of dielectric constant e is related to (k2 ) by the following bination with linear refractive index and WDD single oscillator
relation [17]: model to estimate v(3) value [60]. In the present work, the formula
suggested by H. Tichá et al. which combine Miller’s generalized
e2 N
e ¼ n2 ¼ el  k2 ð12Þ rule and low frequency linear refractive index estimated from
4p 2 c2 e m WDD single oscillator model is used [61,62]:
4
where el is the empty lattice dielectric constant and N/m⁄ is the ratio vð3Þ Aðvð1Þ Þ ð14Þ
of the free-carrier concentration to the effective mass. As shown in
Fig. 9, a linear relation between n2 and k2 is depicted. In Fig. 9, the The linear optical susceptibility for isotropic medium is given
empty dots refer to the experimental results together with the fit- by [61]:
ting to Eq. (12) shown as continuous line. The value of the ratio ðn2  1Þ
(N/m⁄) is obtained from the slope of the straight line while the value vð1Þ ¼ ð15Þ
4p
of el is extracted from the intercept which is given in Table 2. As
shown in Table 2, the value of el is larger than the value of e(1), So from Eqs. (10) and (15) we can obtain the following relation:
so there is a contribution of free charge carriers to the infinite E Ed
dielectric constant. The calculated value of the ratio (N/m⁄) for CdTe vð1Þ ¼ 2
ð16Þ
4p ðE2  ðhtÞ Þ
QDs thin film is found to be 1.3  1047 g1 cm3 while the same ra-
tio for microstructure CdTe is found to be 1.7  1046 g1 cm3 [55]. In the long wavelength limit (ht ? 0 so n = n(1)) we have:
The higher value of the ratio (N/m⁄) for CdTe QDs thin film is may be
Ed =E
attributed to strong electron confinement inside the dots which vð1Þ ¼ ð17Þ
4p
may cause strong electron scattering within the dots conduction
band. This scattering cause an increase in concentration of free car- From previously calculated values of E, Ed, v(1) = 0.1886, so by
riers and this coincide with the fact that there is a contribution of using Miller’s rule Eq. (14) we can obtain v(3) in the limit of
free carrier concentration due to the difference between e(1) and ht ? 0 as follows:
4
AðE Ed Þ4 Aðn2 ð1Þ  1Þ
vð3Þ ¼ 4
¼ 4
ð18Þ
ð4pÞ ð4pÞ
3.5
since A = 1.7  1010 and the value of v(3) (esu) is given in Table 3.
The non-linear refractive index which is related to non-linear sus-
3.4
ceptibility and linear refractive index will be given by the following
relation [53,63]:
n2

3.3
12p2 vð3Þ
n2 ðesuÞ ¼ ðesuÞ ð19Þ
n2 ð1Þ
3.2
where
3.1
8p105
1 2 3 4 5 n2 ðcm2 =WÞ ¼ n2 ðesuÞ ð20Þ
2 2
cn0
(λ) (μ m)
The calculated values of v(3) and n2 are given in Table 3 com-
2 2
Fig. 9. The relation between n and k for CdTe QDs thin film. pared with values microstructure CdTe reported in the literature.
 M.M. El-Nahass et al. / Journal of Alloys and Compounds 604 (2014) 253–259
Table 3
Non-linear susceptibility v(3) and non-linear refractive index n2.
Non-linear parameters CdTe v(3) esu n2 (m2/W)
13
Nanostructure experimental 2.1508  10 2.0797  1018
Microstructure
Ref. [37] 7.2  1010 – Lett. 94 (2009) 063101.
Ref. [48] – 2.4  1017
4. Conclusions
Thermal evaporation technique has been used to prepare CdTe
QDs thin film from CdTe QDs powder which synthesized by using
hot- injection chemical technique. The crystal structure of CdTe
QDs powder and thin film were examined by X-ray technique
indicates the powder and thin film crystallize in the form of cubic
zinc-blende structure with lattice parameter 6.46 Å and 6.45 Å,
respectively. Also a high resolution transmission electron micro-
scope (HRTEM) was used to characterize the nature and the aver-
age particle size of the powder and thin film. The average
particle size found to be 2.5 nm for the powder and 2.7 nm for thin
film. For the as deposited films, direct allowed transition with
energies Eg1 ffi 2 eV and Eg2 ffi 2:3 eV observed from the dependence
2
of ðahmÞ on the incident photon energy which attributed to quan-
tum confinement effect. The lowest transition energy indicates
that the optical band gap of CdTe QDs can be tuned by varying
the particle size. Higher Urbach energy (360 meV) is found com-
pared to microstructure CdTe. Single oscillator model proposed
by Wemple–DiDomenico was used to describe the variation of
the refractive index and refractive index dispersion of the as depos-
ited CdTe QDs thin film. The obtained refractive index is reduced
from 2.66 for microstructure CdTe to be 1.7 for CdTe QDs thin film.
There is a contribution of free charge carriers introduced from that
empty lattice dielectric constant el is larger than the dielectric con-
stant at infinite frequency e1. The ratio N/m⁄ is calculated and dis-
cussed. Finally, some empirical relations were used to calculate
non linear optical parameters.
Acknowledgements
The authors are appreciating so much for M. Emam-Ismail,
assistant professor, faculty of science, Ain Shams University for
his effective discussions and revisions. Also the authors are grateful
to both; E.M. El-Menyawy, researcher, National Research Centre,
and A.A. Attia, assistant professor, faculty of education, Ain Shams
University for their valuable discussion and revision.
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