Current Applied Physics 9 (2009) 12961299

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Current Applied Physics

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

A comparative study of thermal properties of similar Zn-free and Zn-doped

thin lms
Karem Boubaker
Unit de Physique de Dispositifs Semiconducteurs, UPDS Facult des Sciences de Tunis, 63 Rue Sidi Jabeur, 5100 Mahdia, Tunisia

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

Article history: Zn-doped sprayed thin lms have been grown on binary In2S3 substrates under the mean temperature
Received 27 April 2008 (Td = 320 C). Further studies Amlouk et al. [M. Amlouk, M.A. Ben Said, N. Kamoun, S. Belgacem, N. Brunet,
Received in revised form 10 January 2009 D. Barjon, Japan Journal of Applied Physics 38 (1999) 26-30]; Lazzez et al. [S. Lazzez, K. Boubaker, M.
Accepted 19 February 2009
Amlouk, Indirect measurement of Zn-doped In2S3 NANO lms SPECIFIC heat capacity, International
Available online 6 March 2009
Journal of Nanoscience 7 (2008) 15.]; Lazzez et al. [S. Lazzez, K. Boubaker, T. Ben Nasrallah, M. Mnari,
R. Chtourou, M. Amlouk, S. Belgacem, Structural and optoelectronic properties of InZnS sprayed layers,
PACS:
Acta Physica Polonica A 114 (2008) 869880.] investigated the band gap shift, the structural and morpho-
61.72.Vv
68.55.Ln
logical changes induced by this doping. In this study, a quantitative comparative evaluation of the
65.80.+n thermal properties of the as-grown layers is carried out. The obtained results, parallel to further informa-
78.20.Nv tion, plea for the superior thermal efciency of the recently proposed Zn-doped ternary compounds.
2009 Elsevier B.V. All rights reserved.
Keywords:
Zn-doped thin lms
In2S3
Thermal properties
Ternary compounds

1. Introduction chloride and Thiourea on glass substrates. In our previous reports

The Zn-doped IIIV semiconductor layers have been proposed
in the last decades as materials for a wide range of opto-electronic
devices. For example, Xu et al. [4] proposed Zn-doped epilayers
grown by pulsed laser deposition (PLD) on GaAs and Si substrates,
Lee and Lee [5] elaborated optical-active nanocrystalline Zn-doped
thin lms by a chemical method, Sivakumar et al. [6] succeeded to
synthesize multi-use zincFerrite nanocrystals using a new ultra-
sonic cavitation approach, Jeong et al. [7] proposed Zn-doped in-
dium tin oxide anodes for organic electroluminescence devices.
More recently, Kim et al. [8] performed solgel processed porous
Zn-doped thin lms prepared with interesting luminescence prop-
erties. Wang et al. [9] elaborated ZnSe:Li3N grown by a closed
Bridgman method, which consisted of annealing precursors single
crystals at high temperature in a Zn-saturated atmosphere.
The panoply of these original processes and materials [49]
have created new opportunities in the areas of photo-voltaic solar
cells and emitting devices.
In this context, our studied Zn-doped thin lms were obtained
by spraying an aqueous solutions containing indium chloride, zinc
E-mail address: boubaker_karem@yahoo.com
[13], we monitored the growth process of In2S3 and ZnIn2S4 thin
lms by changing the precursor solutions concentration ratio
x = [Zn]/[In], and conjectured the existence of an optimal value of
this ratio (x = 0.33). The alteration of the thermal characteristics
due to zinc incorporation is reported and discussed within a theo-
retical and experimental protocol.
2. Experiment
The photothermal measurements were carried out using an en-
hanced Mirage Effect [1012] disposal (Fig. 1). In this setup, the
studied layer receives an incident heat from a pulsed source. Con-
sequently, the layer acts as a secondary source that heats ambient
uid. Heat ow that moves from the heated surface to the uid in-
duces a refraction index gradient.
The refraction index variations are measured in the ambient
uid, at a constant distance from the layer heated surface by the
mean of a probe beam (Fig. 2), which crosses the prospected area
with a prexed disposition beside targeted surface and geometrical
relative position. The Photothermal Signal Detection (PSD) is a set
of measurements that leads to the determination of the probe
beam response parameters (frequency, amplitude and phase).

1567-1739/$ - see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.cap.2009.02.016
 K. Boubaker / Current Applied Physics 9 (2009) 12961299 1297

where Q(r,z,t) is the source term dened in Eq. (1) and D is the uid
thermal diffusivity.
The solution to Eq. (3), expressed in cylindrical coordinates is
proposed in other studies [1316] as Eq. (4) for surface tempera-
ture expression (z = 0):
p 2
bQ 0 p  2r 2
T s r; z; tjz0  e b kth  ejxt : 4
2k

3.2. PSD phase and amplitude

The normal component wz of the probe beam deection PSD, is

calculated by the relation (5):
 Z 1
1 @Tr; z; t dTr; z; t
wz    dl; 5
n0 @n T0 0 dz

where dl presents probe beam geometrical path and n0 is the mean

Fig. 1. The photothermal technique mounting. refraction index at the temperature T0.
The maximum temperature T0 is calculated using Coulomb
approximation:
 
Q tot 1
T0 C ; 6
2p k r
with:
8 R 1  r22 R 1 z
> 2
> Q tot Q 0 0 e b  2prdr 0 e b dz  Q 0 pb
>
<
R 1  r 2
2
; 7
e b dr p
>
> C1r R 0 bp
>
: 1 r2 
e b2 rdr
0

which gives:
p
bQ 0 p
T 0 T max : 8
2k
In the case of optically thick massive ideal sample heated by
Gaussian beam source; theoretical calculations of probe beam
deection component wz for a small offset z0, which means that
the signal vanishes for the values (z > z0) give (9):
p q
Fig. 2. Disposition. bQ 0 p c c  bh 2
wz b k2th erf z0 h ejxt : 9
2  T 0 k bh  1 cbh 1
Thus, probe beam deection is dened through its two param-
3. Theory
eters: phase /z and amplitude |wz|, Eqs. (10) and (11):
3.1. Heat equation solution wz jwz j  ejxt/z 10
8 q
The heat energy transmitted from the layer to the ambient uid > p   q z0 h pf
>
< jwz j bQ 0 p  ccbh   2 2  Df
per unit volume, and at a pulse frequency f is expressed [13,14] by 2kT 0 bh 1cbh 1
  b kth :e
Eq. (1): ;
>
> n o h i q
: / p Arg ccbh
1
 Arctg Df
 z  h pf
2 z 4 b 2 2 0 Df
2 r 2 jxt  z h 1cbh 1 pf b
Q r; z; t Q Q 0  e b e b e ; 1
11
where Q0 is the nominal heat transmitted from the target to the
k r
bulk uid elementary volume, whose value depends on both uid
g
with c k g
where kg is glass substrate thermal conductivity, rg
qr
and targeted surface thermal parameters, x = 2pf, b is the thermal pf
1 j Dg with Dg: glass substrate thermal diffusivity and
wavelength inside the uid medium, dened by b2 pDffl with D
the uid thermal diffusivity, and b is Gaussian beam external radius. bh e2rh , where h is the studied layer thickness and r
q
The heat equation, inside the uid medium at surface vicinity, is 1 j pDf with D: layer thermal diffusivity.
hence expressed by the equation: In the case of the prospected layers, theoretical calculations of
~ ~ probe beam deection components wz for a small offset z0, give
/ k  gradT; 2
Eq. (12):
where k is the thermal conductivity (W m1 K1) and T(r,z,t) is the p q
absolute temperature (K). bQ 0 p 2
z
 0
wz b k2th  e kthfl ejxt jwz j  ejxt/z ; 12
Eq. (2) leads to Eq. (3): 2k
q
1 @Tr; z; t Qr; z; t with the respective denitions kth D
and kth;fl b dened in
r2 Tr; z; t   ; 3 pf
Dfl @t k (1). Consequently we have:
1298 K. Boubaker / Current Applied Physics 9 (2009) 12961299

Fig. 3. Variations of the PSD amplitude logarithm versus frequency square root.

Fig. 4. Variations of the PSD phase versus frequency square root.

8 r p
q
> p q  22z0 pf
>
< jw j bQ 0 p 4 D2 Dfl
z 2k
b p2 f 2  e p  
  p q : 13 bQ 0 p LnA0 14Ln b4 p2Df2 2 S
>
> k e
: /  p 1 arctan D  2  z0 pf 2
z 4 2 pf b2 2 D
p S s
fl

bQ 0 p e 4 4 D2
 b 2 2: 17
4. The thermal characteristics
2 A0 p  f0
Finally the specic heat capacity C is deduced from Eq. (18):
The experimental variations of the probe beam deection PDS r
p
peS  4 b4 pD2 f 2
2
Ln-amplitude (Ln|wz|), for both Zn-free (x = 0.0) and Zn-doped Q0
(x = 0.33) layers are conjointly presented in (Fig. 3). These varia- k 0
C   ; 18
tions, in addition to the theoretical slope S of the curves for high q  D 2p  A0  f0  b  q  tan 2 /0 p4  S
frequencies, lead to calculation of the thermal parameters.
where q is the density.
p! s " p! r#p
2 pf 2 p The calculated and deduced values are gathered in Table 1.
Lnjwz jjf!1   z0   z0 f From Table 1, it can be seen that ZnIn2S4 ternary material ther-
2 Dfl 2 Dfl
p mal conductivity is 45% lower than the In2S3 binary compound.
S  f; 14 Similarly, Zn-doped compound thermal diffusivity is about 50%
lower than Zn-free one. In the same way, the specic heat capacity
p! r C value decreases less noticeably. This feature, which is in concor-
2 p
S  z0 : 15 dance with (Eq. (18)), and with the values yielded by Kozlowski
2 Dfl
et al. [17] De Otfried [18] and Menon and Philip [19], strengthens
In fact, the calculation of the slope S, deduced from (Eqs. (14) the analyses that privileges ZnIn2S4 to binary In2S3 as a material
and (15)), along with accurate knowledge of the thermal diffusivity for buffer layers. This trend was mainly based, until a recent date,
of the parafn oil uid medium (D = 8.21 m s2), allows obtaining on the fact that the energy band gap of ZnIn2S4 sprayed thin lms is
the offset z0; whose value is difcult to measure experimentally. relatively greater than In2S3 one [2024].
Subsequently, and using (Eq. (14)), we determine the coordi-
nates Ln(A0) and /0 in a particular point M0(f0, Ln(A0),/0). 5. Analyses and conclusion
As the slope S is already known, the value of the thermal diffu-
sivity D of the layer is deduced from the value of /0 (Fig. 4), and Zn-doped thin layers physical characteristics have been a centre
(Eq. (13)). of interest as efcient materials for solar cells buffer layers [17
  p  24]. Many studies investigated their optical, opto-electronic and
2
D p  f0  b  tan 2 /0  S : 16 luminescence properties performances [17,2024] in order to jus-
4
tify their use as an alternative to Cadmium-based binary and ter-
The value of the thermal conductivity k of the layer is then ob- nary compounds.
tained using the lastly calculated value of thermal diffusivity Ds In this study, work, we focused on the thermal properties of
and (Eq. (14)): In2S3 and ZnIn2S4 sprayed thin lms. Photothermal measurements

Table 1
The relevant calculated and deduced values.

Layer values Zn-free layer (In2S3) Zn-doped layer (ZnIn2S4) Unit

Chopping frequency 85 85 Hz
Offset z0 358.2 321.7 lm
Laser beam radius 0.8 0.8 mm
Thermal diffusivity (68.5 8.0)  106 (35.1 5.5)  106 m2 s1
Thermal conductivity 16.5 0.8 7.14 0.7 W m1 K1
The specic heat capacity (521.5 26.0) (503.0 25.5) J K1 kg1
 K. Boubaker / Current Applied Physics 9 (2009) 12961299
were carried out in order to understand the effect of the moderated
introduction of the zinc element in preexistent binary structures.
The thermal conductivity and diffusivity were obtained by bringing
experimental and theoretical results together. It was noticed that
the thermal diffusivity and conductivity of the doped layers de-
creased about 50%. Since solar cells buffer layer material is
supposed to trap the incident energy, we could conjecture that
Zn-doped binary compounds are more appropriate to the constitu-
tion of buffer layers than the classical IIIV and IIVI compounds.
We are testing this conjecture through microstructure analyzes
that may conrm the determinant role of zinc in ternary com-
pound thermal performances enhancement, since the presence of
some other inuent zinc compounds as ZnO [1923] and ZnS
[25] could not totally avoided.
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