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Europium incorporation dynamics and some

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DOI: 10.1016/j.mssp.2015.11.005

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 Materials Science in Semiconductor Processing 43 (2016) 8–16

Contents lists available at ScienceDirect

Materials Science in Semiconductor Processing

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

Europium incorporation dynamics and some physical investigations

within ZnO sprayed thin films
O. Kamoun a, A. Boukhachem a, A. Yumak b, P. Petkova c, K. Boubaker a,n, M. Amlouk a
a
Unité de Physique des Dispositifs à Semi-conducteurs, Faculté des Sciences de Tunis, Université Tunis El Manar, 2092 Tunis, Tunisia
b
Physics Department, The Faculty of Arts and Science, Marmara University, 34722 Göztepe, Istanbul, Turkey
c
Shumen University “Konstantin Preslavsky”, 115 Universitetska str., 9712 Shumen, Bulgaria

art ic l e i nf o a b s t r a c t

Article history: Europium doped ZnO thin films were deposited on glass substrates using a simple mini spray technique
Received 29 August 2015 at 460 °C. The structural properties of as-prepared thin films were characterized by X-ray diffraction
Received in revised form (XRD). Both undoped and Eu-doped films show strong preferred c-axis orientation. The maximum value
31 October 2015
of the volume cells was obtained at 1% doping level. The texture coefficient (TC) of the films along (002)
Accepted 10 November 2015
direction changes with the doping level due to Eu incorporation.
The optical band gap calculated from transmittance and reflectance spectra show the effect of con-
Keywords: centration on this energy. They equally outlined the direct gap absorption of these materials. Analysis of
Zinc oxide Urbach–Martienssen model parameters allows nano-scale explanations of the doping-related divergence
Europium doping
of Urbach tailing evolution.
Optical properties
& 2015 Elsevier Ltd. All rights reserved.
Single oscillator model
Urbach tails
Dielectric constant

1. Introduction
In recent years, transparent conductive oxide (TCO) thin films
have attracted much attention due to their physical properties and
their important applications in the sensors [1–5], light-emitting
diodes [6–8], solar cells [9,10], surface acoustic devices [11–14],
and others [15–17]. The optical properties of these materials can
be easily fine-tuned by controlling contents of the different con-
centrations. Though a great deal of excellent work has been re-
ported on such materials [13–15], it is still meaningful to extend
the research of these TCO thin films.
Despite the amount of research done, zinc oxide (ZnO) remains
a potential candidate to fill the needs of these TCO materials. ZnO
has a broad band gap of about 3.3 eV and a high melting tem-
perature of 2248 K (1975 °C) [18–20] and it presents a window of
transparency in the visible range. These advantages prove that it is
one of the promising candidates in terms of the number of op-
toelectronic applications.
In binary oxides such as ZnO, the incorporation rare-earth
elements in compound and the long life times of the excited states
lead to an easy realization of population inversion with promising
applications in optoelectronic applications. This corroborates with
previously observed photoluminescence in visible red region [21].
n
Corresponding author.
E-mail address: Boubaker_karem@yahoo.com (K. Boubaker).
Among these rare elements, Eu3 þ ion doping has been extensively
studied due to its particular spectral character and application in
red lighting phosphor [22–26]. Indeed, it is reported that Eu-
doped ZnO urchins by biopolymer assisted hydrothermal method
consisting of nano-rods and excited by 325 nm xenon laser emit
white light, which originates from the luminescence of ZnO and
the intra-4f transitions of Eu3 þ ions [27]. Recently, Europium-
doped zinc oxide as powder prepared by hydrothermal process
with a 3% doping ratio showed optimal photocatalytic oxidation. It
is found that the decolorization rate of pharmaceutical wastewater
consists of over 38% degradation rate after treatment under UV
irradiation during 150 min [28–30].
To meet the requirements in different application domains, ZnO
can be doped with a variety of ions [30–32]. Several techniques such
as Organometallic Chemical Vapor Deposition (MOCVD) [33], Chemi-
cal Vapor Transport (CVT) [34], sputtering or spraying [35] and laser
ablation [36,37] have been used to prepare thin films of these types of
transparent and conductive materials to suit the needs of research and
industries. These techniques are generally either sophisticated or ex-
pensive hence the need for a simple, easy and less expensive techni-
que. In comparison with other techniques, the spray pyrolysis method
[38–42] is widely used to prepare oxide thin films. It is also char-
acterized by a uniform size distribution and it provides thin films with
grain size which is controlled by the doping concentration. Further-
more, this technique leads to a large production area and it is special
to give crystallized thin films without recourse to thermal processing
[43–47].

http://dx.doi.org/10.1016/j.mssp.2015.11.005
1369-8001/& 2015 Elsevier Ltd. All rights reserved.
 O. Kamoun et al. / Materials Science in Semiconductor Processing 43 (2016) 8–16 9

For these reasons, we have used the method known as because

it can be easily adapted for film production of large area, as it al-
lows us to have thin films with size grain that we can control by
the doping concentration.
Knowledge of optical constants of materials often presents a
major interest in the design and analysis of materials to be used in
optoelectronics. Optical measurements are widely used to char-
acterize the composition and quality of materials. Thus, it is es-
sential to have an overview of optical properties which include the
optical band gap, reflectivity, absorption coefficient, dielectric
constant and refractive index and the index of extinction as a
prerequisite for the use of a suitable material for applications.
Nevertheless, it is reported that there have been several com-
prehensive studies on the crystal structure and optical transmit-
tance of doped ZnO thin films prepared by spray pyrolysis meth- Fig. 1. XRD spectra for the ZnO:Eu.
ods [48–50]. However, there are few studies on the optical con-
stants, dielectric function, reflection and absorption coefficient of 3. Results and discussion
doped ZnO thin films as well as on the electrical properties of such
films. 3.1. Structural properties:
The present paper seeks to investigate the effect of europium
incorporation on the structural, electrical and optical properties of Fig. 1, is the X-ray diffraction patterns of the zinc oxide films,
ZnO:Eu thin films by the spray pyrolysis technique. These films shows the effect of concentrations of Eu in the spray solution
have been investigated by using XRD, optical reflectance and (y¼[Eu3 þ ]/[Zn2 þ ]).
transmission spectra, PL and Raman spectroscopy. Europium is a X-ray diffraction spectra show well-defined peaks of (100),
valence of þIII element such as indium, the doping by europium (002), (101), (102) and (103), corresponding to hexagonal würtzite
can improve both optical and electrical properties of ZnO. Also, phase according to JCPDS 036-1451 card.
Europium is a rare earth element with an electronic configuration Also, it is noted that the XRD peaks are very narrow showing a
[Xe] 4f76S2. This structure with an occupied orbital f can play an good crystallinity of the prepared thin films.
important role in terms of photoluminescence and open the way The interplanar spacing dhkl values of ZnO thin films were also
for laser based on ZnO material On the other hand, an attempt calculated by using Bragg equation [48–50]:
regarding their electrical properties has been carried out by means
2dhkl sin θ = nλ (1)
of the conductivity measurements in terms of temperature.
In the ZnO hexagonal structure, the plane spacing is related to
the lattices parameters a and b as well as the Miller indices by the
2. Experimental details following relation [48] (Table 1):

2.1. Un-doped and Eu-doped ZnO films preparation
ZnO thin films were first prepared at a glass substrate tempera-
ture of 460 °C, using propanol and zinc Acetate Zn(CH3CO2)2:10  1 M
[47]. The precursor mixture was acidified using acetic acid (pH¼ 5)
and the carrier gas was Nitrogen (pressureE0.35 bar) through a
0.5 mm-diameter nozzle. The nozzle-to-substrate plane distance
was fixed at the optimal value of 27 cm as demonstrated by K.
Boubaker et al. [41]. During the whole deposition process, precursor
mixture flow rate was approximately 4 mL/min.
Under similar experimental conditions, Europium-doped ZnO:
Eu thin films solutions have been fabricated by adding europium
oxide to the precursor solution while maintaining acidity level. In
the elaborated samples, the europium-to-zinc molar ratios
[Eu3 +]
y= were 0%, 0.4%, 0.7% and 1%. after deposition, the films
[Zn3 +]
were cooled to room temperature.
2.2. Characterization techniques
1 4 ⎛ h2 + hk + k 2 ⎞ l2
2
= ⎜ 2
⎟+ 2
dhkl 3⎝ a ⎠ c (2)
The calculated values of the lattices parameters and their ratio
(c/a) of the different ZnO:Eu sprayed thin films are gathered with
the volume unite cells in Table 2.
From calculated value of lattices parameters (Table 2), it is
found that this parameter reaches a high value for 1% Eu doping
level and a minimum for 0.7% of Eu content. These appropriates
doping level can be considered particular for improving some
physical properties of such doping II–VI binary thin films. Indeed,
in comparison with other doping level, the compactness of the
host material has a maximum value at this special [Eu]/[Zn] ratio,
this can pave the way for high interaction of this 0.7% Eu-doped
ZnO oxide against photon light and electric response as well as
sensitivity applications.
Regarding the X-ray spectra of the ZnO:Eu thin films, it is found
the intensities of the XR diffraction decrease with Eu concentra-
tion, this is related to the influence of various factors such as the
spray temperature, flow rate of the sprayed solution and

The structural analysis of obtained thin films was carried out Table 1
using X-ray apparatus (Philips PW 1729 system) using Cukα Lattice parameters of ZnO:Eu thin films.
monochromatic radiation (λ ¼0.15405 nm). The optical transmit-
a (Å) c (Å) Volume (Å3) c/a
tance T(λ) and reflectance R(λ) of ZnO:Eu sprayed thin films were
recorded using a Perkin Elmer Lambda 950 spectrophotometer in a ZnO 3.2413 5.1915 47.2346 1.6017
250–2500 nm wavelength domain, while Raman spectra were ZnO:Eu 0.4% 3.2418 5.1887 47.2239 1.6006
ZnO:Eu 0.7% 3.2397 5.1887 47.1610 1.6016
measured using HORIBA Jobin yvon spectrometer Raman LABRAM
ZnO:Eu 1% 3.2474 5.2058 47.5423 1.6031
HR with He–Ne 632.8 nm excitations.
10 O. Kamoun et al. / Materials Science in Semiconductor Processing 43 (2016) 8–16

Table 2 3.2. Optical properties of the crystalline ZnO thin film

Different texture coefficient TC(hkl) values of ZnO:Eu.
3.2.1. Band gap energy calculation
TC (ZnO) TC (ZnO:Eu 0.4%) TC (ZnO:Eu 0.7%) TC (ZnO:Eu 1%)
The optical transmission and reflectance spectra of the ZnO:Eu
(100) 0.295 0.383 0.323 0.4297 sprayed thin films grown on glass substrates are shown in Fig. 2.
(002) 6.097 6.094 5.533 3.769 The spectra show a high transmittance of all thin films, higher
(102) 0.171 0.155 0.717 0.224
than 80% and low reflectance less than 25% accepted to free ZnO
(110) – 0.106 0.159 0.138
(103) 0.236 0.162 0.176 0.205 which is probably to some defect. This phenomenon can be at-
(112) 0.095 – – 0.122 tributed to less scattering effects, structural homogeneity and an
(004) 0.105 0.097 0.090 0.089 improvement of the crystalline state. Besides, the presence of the
interference phenomenon indicates a smooth and homogeneous
surface of all observed films
spontaneous cooling. In this case, it may happen that the crystal-
The film thickness was measured by the optical method [54–
lites are oriented, not completely random, but preferably in one or
56]:
more particular directions.
It follows that the material has a texture. This effect is studied p p+1
1 λ max λ max
d=
through texture coefficient using the following relation [48–51]: p p + 1 p+1
2 n (λ max ) λ max − n (λ max p
) λ max (7)
I (hkl)/I0 (hkl)
TC(hkl) = −1 where n(λpmax) is the refractive index associated with the wave-
N ∑ I (hkl)/I0 (hkl) (3) length giving maximum reflection of order p (p integer) in the area
where I(hkl) is the measured relative intensity of (hkl), I0(hkl) is the of low absorption value and it can be calculated by using the fol-
standard intensity of the plane (hkl) taken from JCPDS 036-1451 lowing relationship [54–58]:
card and N is the reflexion number. The calculated texture coeffi-
1+ Rmax
cient are listed in Table 2. n (λmax ) = n 0 ns
These results reveal the existence of a preferred orientation 1− Rmax (8)
within (002) plan for different concentration of europium. n0 and ns are respectively the optical indices of air (n0 ¼1) and
It is found that all Eu-doped ZnO thin films had the highest
substrate; the thickness of the obtained ZnO thin films are in 0.5–
(002) diffraction peak intensity indicating that (002) is the pre-
0.52 mm domain.
ferential orientations. Also, the TC value of (002) orientation de-
creases with the Europium content. This result may be related to
3.3. Impact on the optical bandgap and Urbach energy
the ionic radius difference of Zn2 þ (74 pm) are smaller than Eu3 þ
(94.7 pm) [52].
The fundamental absorption edge of the films corresponds to
Moreover, XRD spectra were used to study the effect of in-
corporation of the element Eu in the ZnO matrix respectively on transitions of electrons from the valence band to the conduction
the crystallite size, using the formula Deby–Scherrer [39,48,53], band edge and this can be used to calculate the difference in the
the stress [53] and dislocation density [39,53] optical band gap of the films. The absorption coefficient can be
expressed by [59,60]:
k. λ
D=
β1 cos (θ ) 1 ⎛ (1 − R)2 ⎞
2 (4) α= Ln ⎜ ⎟
d ⎝ T ⎠ (9)

In the case of a direct transition, the absorption coefficient and

β1 optical band gap are related by the following relation
2
ξ= [38,51,61,62]:
4 tan (θ ) (5)
1
αhν = ⎡⎣ A (hν − Eg ) ⎤⎦ 2 (10)
1
δ= 2 where A is a constant, hν is the photon energy and Eg is the optical
D (6)
band gap. Fig. 3 shows the plot of [α.(hν)]2 versus the photon
where k¼ 0.90 is the Scherrer constant, β1/2 ¼corrected half width energy hν which yields in the sharp absorption edge for the high
of the peak and λ ¼ 1.54 Å is the wavelength of CuKα radiation. quality films by a linear fit. The calculated values of optical band
These parameters are calculated along the preferred (002) or- gap Eg of Eu-doped ZnO are summarized in Table 4.
ientation their values are gathered in Table 3. In addition, optical absorption by defects also appears at energy
From this structural study, it is found a particular effect for 1% lower than optical gap which can create, interactions with pho-
[Eu]/[Zn] ratio. Indeed, for low doping, the high value of lattice nons increases and therefore the formation of band tailing in the
parameter c of the hexagonal structure was obtained for 1% doping band gap. Mott et al. [63] note that unlike crystalline structures
level (see Table 1). This same doping level gives the less crystallite where the fundamental edge is mainly determined by conduction
size and the strong value of both stress and dislocation density. and valence levels, ion-doped binary semiconductor compounds
present a particular optical absorption edge profile. In these ma-
Table 3 terials, the absorption coefficient profile increases exponentially
Dislocation density of ZnO:Eu thin films. with the photon energy near the energy gap. This variation results
D (nm) ξ (10  4) δ (1014 lines/m2)
in “blurring” of the valence–conduction bands and narrows
slightly the band gap by appearance of the so-called Urbach
ZnO 60.8 19.2 2.7 tailing.
ZnO:Eu 0.4% 74.1 15.7 1.8 Regarding these interactions, α is written as another ex-
ZnO:Eu 0.7% 63.7 18.3 2.4
ponential function of photon energy which follows the empirical
ZnO:Eu 1 % 44.4 26.3 5.1
Urbach law [64–66]:
 O. Kamoun et al. / Materials Science in Semiconductor Processing 43 (2016) 8–16 11

100 40

35
ZnO
80
Transmittance (%)
30 ZnO:Eu 0.4%

Reflectance (%)
25 ZnO:Eu 0.7%
60
ZnO ZnO:Eu 1%
20
ZnO:Eu 0.4%
40 ZnO:Eu 0.7% 15
ZnO:Eu 1% 10
20
5

0 0
500 1000 1500 2000 2500 500 1000 1500 2000 2500
wavelength (nm) wavelength (nm)
Fig. 2. Transmittance and reflectance spectra of ZnO:Eu thin films.

Table 5
Opto-thermal expansivity ΨAB values.

sample ZnO ZnO:Eu 0.4% ZnO:Eu 0.7% ZnO:Eu 1%

ΨAB(  10  12 m3 s  1) 19.70 16.44 18.00 17.06

⎛ hν ⎞
α = α0 exp ⎜ ⎟
⎝ EU ⎠ (11)

where α0 is a constant and EU is the Urbach energy which char-

acterizes the slope of the exponential limit, Fig. 4.
The value of EU is obtained from the inverse of the slope of Lnα
vs. hν [55] using the following relation [41,65,66]:
Fig. 3. Plot of (αhν)2 versus photon energy of ZnO:Eu thin films. ⎡ dLnα ⎤−1
EU = ⎢ ⎥
⎣ dhν ⎦ (12)

EU values are given in Table 4.

Table 4 It is found that the Urbach energy decreases with the [Eu]/[Zn]
The band gap and Urbach energy value of ZnO:Eu thin films.
ratio this suggests the decreases of defects. This is probably related
Eg (eV) Eu (meV) to disappear of interstitial zinc atom by Europium doping. The Eu
doping can causes the reorganization of ZnO structure.
ZnO 3.21 113.5
ZnO:Eu 0.4% 3.19 113.5
3.3.1. Opto-thermal investigation
ZnO:Eu 0.7% 3.25 101.8
ZnO:Eu 1% 3.24 104.3
Opto-thermal properties of ZnO:Eu thin films were investigated
through the Amlouk–Boubaker opto-thermal expansivity ΨAB [67–
75]. This parameter has been defined by Eq. (13):
D
ΨAB =
α^ (13)
1240 310
18 (nm) where D is the thermal diffusivity, as deduced from the related
literature [73–75], and α^ is the effective absorptivity.
ZnO
The effective absorptivity α^ is defined as the mean normalized
ZnO:Eu 0.4% absorbance weighted by I (λ )AM1.5, the solar standard irradiance,
16 ZnO:Eu 0.7% with λ: the normalized wavelength:
ZnO:Eu 1%
Ln( )

λ max
∫λ I (λ )AM1.5 × α (λ ) dλ
α^ = min
λ max
14 ∫λ I (λ )AM1.5 d
min (14)

where λmin and λmax are the limit of the visible spectrum and
where: I (λ )AM1.5 is the Reference Solar Spectral Irradiance.
12 Table 5 summarizes the calculated values of ΨAB of ZnO:Eu
1.0 1.5 2.0 2.5 3.0 3.5 4.0 spray thin films.
h (eV)
From these calculated values of opto-thermal expansivity, it can
Fig. 4. Plot of Ln(α) versus hν. be seen that Eu doping results in a slight irregular decrease of the
12 O. Kamoun et al. / Materials Science in Semiconductor Processing 43 (2016) 8–16

opto-thermal expansivity. The maximum value of ΨAB is obtained absorption spectral range, is carried out of some other optical
for 0.7% Eu doping level this is consistent with the suggestion constants based on Wemple–DiDomenico single-oscillator model
mentioned above. [77–79]:
In comparison with previous work it is found that ΨAB of ZnO:
E0 Ed
Eu are higher than ΨAB of than those obtained earlier for ZnO: In n2 = 1 +
E02 − E2 (18)
(12.9 10  12 m3 s  1) ZnO: Yb (8.2 10  12 m3 s  1) and ZnO: Mo(15.2
10  12 m3 s  1) [38]. This property is interesting for possible op- where E¼ hυ is the incident photon energy, E0 is the energy of the
toelectronic applications of ZnO:Eu thin films by reducing the effective dispersion oscillator, and Ed is the dispersion energy.
absorption in solar cells. Wemple–DiDomenico parameters are given in Table 6.
From these calculated values of both Cauchy and Wemple and
3.4. Refractive index and extinction coefficient Di-Dominico parameters, it is found that the particularity of 1%
Europium doping level in terms of Cauchy parameter A and os-
Refractive index and extinction coefficient are the most im- cillator energy related to Wemple and Di-Dominico model. This
portant parameters of optical materials and their applications. confirms the observation mentioned in the structural section
Thus, it is important to determine these two optical parameters of about the crystallites recorded orientation preferably in one par-
the deposited thin films. The optical characteristics of dispersion n ticular direction.
(λ) and k(λ) (refractive index and extinction coefficient, respec-
tively), for values of the wavelength λ between 300 and 1800 nm, 3.5. Determination of complex dielectric functions and oscillator
have been calculated using optical experimental measurements energy.
and the method of Belgacem et al. [42] and Bathe et al. [76]. The
present research is based on the resolution of the following system The complex dielectric constant (ε(ω) ¼ ε1(ω)-iε2(ω)) char-
of nonlinear equations: acterizes the optical properties of the solid material. The real and
R exp (n, k, λ ) − Rtheo (n, k, λ ) = 0 (15) imaginary parts of dielectric constant for pure and doped ZnO
with In and Yb with different concentrations are also determined
Texp (n, k, λ ) − Ttheo (n, k, λ ) = 0 by the following relations [48]:
(16)
ϵ(λ ) = (n (λ ) − ik (λ ))2 = ϵ1(λ ) − iϵ2 (λ ) (19)
Rtheo and Rexp represent respectively the theoretical and ex-
perimental reflectance and, Ttheo and Texp represent respectively
the theoretical and experimental transmittance. ϵ1(λ ) = n (λ )2 − k (λ )2 (20)
The plots of n(λ) and k(λ) are presented in Fig. 5.
For all films, we find that the values of the extinction coefficient ϵ2 (λ ) = 2n (λ ) k (λ ) (21)
(Fig. 5a) in the ultraviolet region are larger than those in the visible
Fig. 6 shows the variation of ε1 and ε2 vs wavelength.
range.
These results can be used in order to determine the optical
The refractive index (Fig. 5b) has hyperbolic decreases with the
constants: ε1, ωp and τ which respectively represent the dielectric
wavelength along the Cauchy distribution [38,41,77] was observed
in all thin films of ZnO:Eu
Table 6
B Values of Cauchy and Wemple and Di-Dominico parameters.
n=A+ 2
λ (17)
A B E0 Ed
where A and B are the Cauchy's parameters and λ is the wave-
ZnO 1.62344 0.44692 2.816 9.408
length of the light used, implying that the films have normal ZnO:Eu 0.4% 2.31104 0.20675 3.745 18.949
dispersion for the entire range of wavelength studied. The values ZnO:Eu 0.7% 1.90019 0.25021 3.544 13.453
of A and B are given in Table 6. ZnO:Eu 1% 1.59783 0.30708 3.288 9.899
Likewise, the hyperbolic decreases of the refractive in the low

Fig. 5. extinction coefficient (a) and variation of refractive index (b) with wavelength.
 O. Kamoun et al. / Materials Science in Semiconductor Processing 43 (2016) 8–16 13

10 0.3

ZnO
8 ZnO:Eu 0.4% ZnO
ZnO:Eu 0.7% 0.2 ZnO:Eu 0.4%
ZnO:Eu 1% ZnO:Eu 0.7%

2
6 ZnO:Eu 1%
1

0.1
4

2 0.0
500 1000 1500 2000 2500 500 1000 1500 2000 2500

(nm) (nm)

Fig. 6. Variation of the real part (a) and imaginary part (b) of complex dielectric constant with wavelength.

constant at high frequencies, the pulse plasma and relaxation time III) oxide lattice along with that the host matrix Eu2O3 (Fig. 7),
by using the following relations [80–82]: were interpreted in terms of conventional lattice-linked para-
meters (Length, vibration parameters, lattice constants, config-
ϵ∞ωp2
ϵ1 ≈ ϵ∞ − λ2 urations, angles and bond spatial extent, etc.).
4π 2c2 (22)
This last fact, which resulted in less Eu incorporation, can jus-
tify the recession of physical enhancement for doping amount
ϵ∞ωp2
ϵ2 = 2nk ≈ λ3 around 0.5%. In fact, and in concordance with the earlier records of
8π 3c3τ (23)
Petkova [83] et al. and Boubaker et al. [84] concerning similar
compounds, the host lattice structure main parameters differ
4πNe2
ωp2 = drastically from those of the intrinsic doping element oxide.
ϵ∞me* (24) Europium ion incorporation is hence not enabled, in the sense of
The calculated values of these constants are gathered in Table 7. the Lattice Compatibility Theory.

4. Lattice Compatibility Theory investigation 5. Raman effect investigation

The Lattice Compatibility Theory, as mentioned in some recent
studies [83–86], is based on the interaction of doping-element
lattice behavior versus host edifice.
Preludes to this theory have been established by Petkova et al.
[83] in the context of analyzing Urbach tailing controversial be-
havior in some nano-compounds as well as I-III-O2 ternary oxides
instability at low temperatures. It was also confirmed by Boubaker
et al. [84–86] on the bases of investigation on some copper-doped
compounds. An original formulation of the Lattice Compatibility
Theory [83–86] has been established as following:
“The stability of doping agents inside host structures is favorized
by geometrical compatibility, expressed in terms of matching
patterns between doping agent intrinsic lattice and those of the
host”.
In the actually discussed case (pure and Eu-doped ZnO), the
nature of the highest occupied bands, and the location of the re-
ciprocal ions Eu3 þ within ZnO lattice structures have been de-
monstrated to be relevant. In this context, fundamental geome-
trical observations concerning the structure of intrinsic (Europium
Table 7
Values of the dielectric parameters deduced from optical measurements.
ε1 ωp (1014 rd s  1)
ZnO 5.104 5.550
ZnO:Eu 0.4% 6.630 3.122
ZnO:Eu 0.7% 6.247 8.615
ZnO:Eu 1% 4.993 6.256
The Group theory shows that Γ = A1 + 2B1 + E1 + 2E2, where B1
corresponds to silence mode A1, E1 and E2 are Raman active modes.
A1 and E1 are polar and infrared active modes; they correspond to
transverse-optical (TO) and longitudinal-optical (LO) phonons re-
spectively. The E2 mode is referred to two modes of low and high
frequency phonons [87].
Fig. 8 shows the Raman spectra performed at room tempera-
ture of the undoped ZnO thin films, followed by those of gradually
Eu:doped ones (Figs. 9–11). First, the observable Raman peak at
109 cm  1 corresponds to non-polar optical phonon modes E2LOW.
It has the highest intensity for ZnO:Eu 1 at% thin film. This result is
similar to that obtained previously by Rajeh et al. [88]. Second,
peak located at 350 cm  1 can be attributed to A1TO mode.wile
peak situated at 448 cm  1 corresponds to ZnO nonpolar optical
phonons of E2high mode [89,90]. In the same line, small Raman
peaks assigned at 495 and 594 cm  1 for ZnO:Eu 1 at%, are related
to 2 LA and E1LO modes respectively [91,92]. The E1LO peak may be
due to O-vacancy defects and also to Zn interstitial states and free
carriers in ZnO:Eu as reported elsewhere [92,93]. Finally, The peak
located at 1150 cm  1 for ZnO and ZnO:Eu 0.4% shift toward low
wavelength by increasing the Eu content. This peak can be at-
tributed to 2A1LO which is similar to one obtained by Ya-Ping et al.
[87] and discussed by Yang et al. [94].
τ (10  14 s)
Since the molar mass of europium is higher than that of zinc
4.511 and since that energy is proportional to the square root of the
0.038 reduced mass, we can find in mass increase per unit volume, a
2.228
simple and plausible explanation to the recorded Raman peak shift
0.319
at low frequencies (Figs. 8–11).
14 O. Kamoun et al. / Materials Science in Semiconductor Processing 43 (2016) 8–16

Fig. 7. LCT synoptic scheme for Eu-doping kinetics within ZnO films.

ZnO 2652
108 ZnO:Eu 1%

448
109

12000
intensity(a.u)
449

1335
intensity(a.u)

1146

350 2LA TA+LO 1262

495
594 684
4000 6000
1140
216
344

E2(high)
2E2low E1(LO)
E2low E (high)-E (low)
2 2
0
0 500 1000 1500 2000 2500 3000 3500 0 200 400 600 800 1000 1200
Raman shift (cm-1 ) -1
Raman shift (cm )
ZnO Fig. 9. Raman spectra performed at room temperature for (1%) Eu-doped ZnO thin
films.

6000 109
ZnO:Eu 0.7% 1146
intensity(a.u)

449 1146 12000

2A1LO
4000
intensity(a.u)

344 8000
386
E2(high) 98
E (high)-E2(low)
E2low2
2000
4000 A1TO
0 500 1000 1500 2000 E2low
Raman shift (cm-1 )
Fig. 8. Raman spectra performed at room temperature for undoped ZnO thin films. 0
0 200 400 600 800 1000 1200
-1
6. Conclusion Raman shift (cm )
Fig. 10. Raman spectra performed at room temperature for (0.7%) Eu-doped ZnO
Eu doped-ZnO thin films deposited on glass substrates have thin films.
been successfully fabricated by spray pyrolysis. Optical properties
of these thin films have been determined using UV–vis-NIR transmittance and reflectance spectra. The real (n) and imaginary
spectroscopy. (k) parts of the complex refractive index were determinate. The
The optical band gap of these films has been calculated. The dispersion of the films was studied using the Wemple–DiDome-
optical absorption spectra show that the absorption mechanism is nico method. The oscillator energy E0 and the dispersion energy Ed
a direct transition. Moreover, the tail absorption follows the Ur- were deduced. The real and imaginary parts of dielectric constant
bach rule. The basic optical properties and optical constants of the for pure and doped ZnO with Eu were also determined by the
Eu-doped ZnO thin films have been investigated by means of following relations and optical parameters were determined.
 O. Kamoun et al. / Materials Science in Semiconductor Processing 43 (2016) 8–16
ZnO :Eu 0.4%
1149
20000 1335
intensity (a.u)
2E1(LO)
447
109
10000
E2(high)
E2low
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Raman shift (cm-1)
Fig. 11. Raman spectra performed at room temperature for (0.4%) Eu-doped ZnO
thin films.
Thin films of Eu-doped ZnO can be very promising and are
subsequently a great potential in the field of optoelectronics.
Nevertheless, the presented results are not the most extensive
reported, we considered that these films are potentially attractive
to be applied as optoelectronic devices. These oxides are destined
to replace the presently used ZnO.
This study reveals that Eu-doping enhances optical properties.
It is known that Indium doping improves the electrical perfor-
mance of ZnO sprayed thin films. Some works based on In–Eu co-
doped ZnO are in progress to improve both optical and electrical
properties.
Acknowledgment
The corresponding author, Pr. Dr. Ing. Karem Boubaker, would
express here, on behalf of all the authors, particular gratefulness’s
to H.E. Mihail Nikolovski, Bulgarian Ambassador in Tunis; and H.E.
Krassimir Petrov, Plenipotentiary Minister, with all the honourable
staff of the Bulgarian embassy in Tunis, for helpfulness and moral
supply. Particular thanks are also addressed H.E. Ömer Gücük, the
Turkish Ambassador in Tunisia, along with his colleagues, mainly
Mr. Erol Toraman and Mr. Ümit Öktem, for support and hints.
Appendix A. Supplementary material
Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.mssp.2015.11.005.
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