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Energy Procedia 84 (2015) 214 – 220

E-MRS Spring Meeting 2015 Symposium C - Advanced inorganic materials and structures for
photovoltaics

Electrical study of Si/PS/ZnO:In solar cell structure

H. Belaida, M. Nouiria, Z. Ben Ayadia, K. Djessasb, L. El Mira,c,*
a
Laboratory of Physics of Materials and Nanomaterials Applied at Environment (LaPhyMNE), Gabes University, Faculty of Sciences in Gabes,
Gabes, Tunisia.
b
Laboratoire de Mathématiques et Physique des Systèmes (MEPS), Université de Perpignan, 52, avenue Paul Alduy, 66860 Perpignan Cedex,
France.
c
Al Imam Mohammad Ibn Saud Islamic University (IMSIU), College of Sciences, Departement of Physics, Riyadh 11623, Saudi Arabia.

Abstract

Indium doped zinc oxide (IZO) thin films have been grown on porous silicon, in order to develop solar cell structure, by
rf-sputtering at room temperature using indium (4 at %) doped nanocrystalline powder previously synthesized by the sol-gel
method. Such layers are polycrystalline with a hexagonal wurtzite structure with a thickness of about 400 nm and preferential
orientation in (002) crystallographic direction. Electrical study under illumination reveals that this type of nanostructure is
promising for solar cell application. By comparing Si/PS/IZO and Si/PS/ZnO/IZO structures, we illustrate a satisfactory
photovoltaic conversion with these structures. Also we reveal that interposing an undoped ZnO layer leads to a degradation of PV
parameters, specially the short-circuit current (Isc) was affected. In fact, Isc decreases from 3 mA to 0.8 mA by adding the
undoped ZnO thin layer. The open circuit voltage is less affected. A decay of 30 mV was recorded. C-V analysis gave a carrier
density of about 1016 cm-3 for both cells.

©
© 2015
2015TheTheAuthors. Published
Authors. by by
Published Elsevier Ltd.Ltd.
Elsevier This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of The European Materials Research Society (E-MRS)
Peer-review under responsibility of The European Materials Research Society (E-MRS)
Keywords: Nanostructure, Zinc oxide, porous silicon, solar cells, sputtering.

* Corresponding author. Tel.: +21697408756; fax: +21675392421.

E-mail address: Lassaad.ElMir@fsg.rnu.tn

1876-6102 © 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of The European Materials Research Society (E-MRS)
doi:10.1016/j.egypro.2015.12.316
 H. Belaid et al. / Energy Procedia 84 (2015) 214 – 220 215

1. Introduction

Transparent conductive oxide films (TCOs) have been extensively investigated due to their broad range of
applications such as transparent electrodes in solar cells and in photovoltaic devices [1,2]. Most TCOs are based on
SnO2, In2O3, ZnO and their mixed compounds. Among the available TCOs, ZnO reveals itself as a potential
candidate for optoelectronic applications, and especially for solar cell, where it is used as a transparent and
conducting top layer. Zinc oxide is II–VI compound semiconductor with wide direct band gap of 3.37 eV and large
exciton binding energy of 60 meV [3] at room temperature, with high transmittance in the visible, exceeding 90%,
and a low resistivity, ranging from 103 to 104 Ω.cm for undoped ZnO films [4]. Undoped ZnO is usually an n-type
semiconductor due to the presence of unintentionally introduced donor centres, usually identified as zinc interstitials
or oxygen vacancies. However, experiments have been inconclusive as to which of these is the predominant defect
[5]. Indium, as well as aluminum, is used for intentional n-type doping. Many different techniques have been used in
the preparation of ZnO thin films, such as physical vapour deposition (PVD) [6], metal-organic chemical vapour
deposition (MOCVD) [7], spray pyrolysis [8], sputtering [9], pulsed laser deposition (PLD) [10], ink-jet printing
[11], electrochemical deposition [12], sol-gel technique [13]. Day by day this last technique is gaining territory in
the synthesis of nanoparticules, due to several advantages: easily proportion and low cost. The essential novelty in
our work is the coupling of the sol-gel and sputtering techniques. The sputtered target is a pellet of a ZnO sol-gel
nanoparticules [14]. Earlier work resolves structural and electrical properties of thin film ZnO onto glass substrates
[15]. The integration of silicon (Si) based structure allows for new opportunities. ZnO/Si heterojunction are of
particular interest in optoelectronic devices. Much work has already been presented about ZnO thin layer elaboration
onto Si substrates [16]. They reported several difficulties caused specially by the large lattice mismatch between Si
and the ZnO layer and the formation of amorphous SiOx layers [17]. Ajimsha et al. [18] reported the electrical
characteristics of n-ZnO/p-Si heterojunction diodes grown by PLD at different oxygen pressures. Kumar et al. [19]
characterized sol-gel derived yttrium-doped n-ZnO/p-Si heterostructures. As we know, a very limited number of
published studies of the properties of ZnO thin films on PS substrates [20]. The application of porous silicon PS in
the field of optoelectronics attracted a great deal of attention. Heterostructures based on porous silicon PS/TCO
junction have been attracted a high interest since they exhibit a wide range of properties, such as light emission from
a PS/SnO2 junction [21]. It was reported in this work that the electrical contact take place in the volume of the PS
film, which improve the electroluminescence efficiency [22]. In our previous work we have presented the
PS/ZnO:Al3% junction as a promising solar cell [23].
This paper focuses on the electrical characterization and the photovoltaic parameters of solar cell based on
n-IZO/p-PS heterostructure. We present two structures: IZO/PS and IZO/ZnO/PS. We reveal the effect of
interposing of the undoped ZnO as a buffer layer between IZO and PS layers on the photovoltaic efficiency.

2. Experimental details

2. 1. Sample preparation

The nanocristalline IZO powder were prepared by the sol-gel method using 20 g of ZAD
[Zn(CH3COO)2 .2H2O] as precursor in a 140 ml of methanol [CH 3OH :99,8%]. After 10 min of magnetic stirring at
room temperature, adequate quantity of [InCl3], corresponding to [In]/[Zn] ratio between 0.01 to 0.05, was added.
After few min magnetic stirring, the solution was placed in an autoclave and dried under supercritical conditions of
ethyl alcohol (EtOH). Further experimental details can be found elsewhere [24-28].
IZO thin films were deposited on p-type porous silicon by rf-magnetron sputtering (13.56 MHz). The sputtering
chamber was evacuated to a base pressure of 2–3×10−4 Pa before admitting the sputtered high purity argon gas
216 H. Belaid et al. / Energy Procedia 84 (2015) 214 – 220

(99.9999%) without oxygen. The sputtering targets were prepared from the aerogel powder of ZnO:In as described
in the first step.
The silicon substrate was etched in a 10% HF for 5 min in order to remove the eventual oxide layer that may form
during stirage, then rinsed in deionized water and dried in N 2 atmosphere. During the sputtering process, for each
sample (Table 1) the substrate was set at room temperature, and the target to-substrate distance was 75mm.

Table 1. Sample codes of the investigated cells.

Code Type of solar cell structure
SCT1 Si(p) / PS / ZnO:In(4%) / ITO
SCT2 Si(p) / PS / ZnO / ZnO:In(4%) / ITO

Porous silicon wafer was prepared with the vapour etching (VE) technique [29], using a phosphorus-doped (100)
oriented Si substrate (ρ = 2 Ω.cm, ND = 5×1015 cm-3) with mirror-polished surface. The VE method involves
exposing a Si substrate to acid vapours issued from a mixture of HNO3 and HF having a concentration of 65% and
40%, respectively. In order to obtain homogeneous PS layer, we need to control the HNO 3/HF volume ratio, the
distance between the silicon substrate and the acid solution in the container, the temperature of the acid mixture and
the exposure time of the Si substrate to the acid vapors.

2. 2. Characterization

The crystalline structure and phase purity of the aerogel were investigated by XRD using the Cu K α
radiation (λ = 1.5418 Ǻ) of a Bruker D5005 diffractometer. Typical θ-2θ spectra were collected between 2θ = 20°
and 70° in 0.02° steps. The surface morphology of ZnO thin layer was investigated using atomic force microscopy
(AFM, TopoMetrix). Current–voltage measurements were performed using a computer controlled set-up comprising
a Keithley 220 current source and an Agilent 34401A multi-meter. To illustrate photovoltaic conversion of our
proposed structures, we used simply an ordinary tungsten lamp placed at a fixed distance. Data was saved after 5
min to ensure an optimal efficiency of the investigated cells. C-V measurement was performed using an Agilent
4294A impedance analyzer.
The aim of this work is to compare two proposed solar cell structures, specified in Table 1. We deduce from photo-
I(V) characteristic the effect of interposing a thin undoped ZnO layer between the PS and IZO layers.

3. Results and discussion

Fig.1. shows the XRD spectrum of the nanoparticles of IZO as elaborated in the first step for the different
In concentrations from 1 at% to 5 at% .Seven pronounced diffraction peaks appear in the 10–70° 2θ range, which
can be attributed to the (100), (002), (101), (102), (110), (103) and (112) planes of ZnO [30]. This result indicates
that ZnO:In nanopowder has a polycrystalline hexagonal wurtzite structure. The average grain size was calculated
using Scherrer’s formula [31]:

0,9O
G (1)
B cosT B
 H. Belaid et al. / Energy Procedia 84 (2015) 214 – 220 217

where λ is the X-ray wavelength (1.78901 Å), θB is the maximum of the Bragg diffraction peak and B is the
linewidth at half maximum (in radians). The average grain size of the basal diameter of the cylinder-shape
crystallites varies from 14 nm to 20 nm, whereas the height of the crystallites varies from 20 nm to 30 nm.

Fig. 1. X-ray diffraction of IZO aerogel nanoparticles.

Fig. 2. shows typical XRD spectra of doped ZnO thin films on PS substrate deposited by rf-magnetron
sputtering. Thin film exhibit an intensive (002) XRD peak, indicating that they have c-axis-preferred orientation due
to the self-texturing mechanism as discussed by Deng et al. [32]. They concluded that film crystal orientation is
caused by minimization of the crystal surface free energy as well as by the interaction between the deposited
material and the substrate surface. The 2T value of the diffraction peak (002) is located at 33.46°, which is very
close to standard ZnO crystal. A small displacement of the (002) peak position was observed compared to the same
peak in the powder, indicating that some residual stress inside the film may exist [33,34].

100
T ZnO
(002)

U Si
(400)

80
T
U
Intensity (a. u.)

60

40

20

0
20 30 40 50 60 70
2TCu (degree)

Fig. 2. Typical X-ray diffraction of doped ZnO thin film deposited on porous silicon substrate by rf-magnetron sputtering.
218 H. Belaid et al. / Energy Procedia 84 (2015) 214 – 220

CV measurement at room temperature confirms the establishment of a pn junction through the

structure. The voltage dependence of the capacitance is displayed as Mott-Schottky plot in Fig. 3. We deduce a
carrier density about 1016 cm-3. This value leads us to confirm that the depletion region is established, especially
through the porous silicon layer.

7,0

6,5
C (10 nF cm )
-2

6,0
-3

5,5
-2

5,0

4,5

-2,0 -1,5 -1,0 -0,5 0,0

Bias (V)

Fig. 3. Mott-Schottky plot of the capacitance of SCT2 solar cell structure.

Fig. 4. Illustrates the dark and the light J–V characteristics of the investigated structures. Corresponding
curves show similar shapes to each other. Dark measurements demonstrate a good rectifying behaviour,
characterized by a rectifying ratio RR about 32 and 8, with SCT1 and SCT2 structures respectively.

(a) Obscurity (b) 1.5 Obscurity

Illumination Illumination
Current density (mA/cm )

4
2
Current density (mA/cm )

1.0
2

0.5
2

-100 0.0 0 100 200 300 400

0
-0.5
-200 0 200 400

-1.0
-2

-1.5
-4
-2.0

Polarisation (mV) Polarisation (mV)

Fig. 4. J-V characteristics for (a): SCT1; (b): SCT2 structures.

Photo-J(V) characteristics show an obvious photovoltaic effect with the two proposed structures. The open circuit
voltage is about 150 mV for SCT1 structure. By interposing an un-doped ZnO layer a decay of 30 mV was recorded.
 H. Belaid et al. / Energy Procedia 84 (2015) 214 – 220 219

The same trend was found with the short-circuit current, but it is more pronounced. J SC is about 5.5 mA/cm2 for
SCT1 and 1.75 mA/cm2 for SCT2, corresponding to a decrease of about 68%. It is noteworthy, with SCT2, that the
light-curve intersects the dark-one, known as the crossover behaviour. This trend was reported by several authors.
This can be related to defect centres at the ZnO/PS interface caused by the dangling bonds, since the large lattice
mismatch between ZnO and Si. Thereby, recombination at the interface takes place and then limits the photo-current
through the cell structure. Additionally, we remark, with SCT2, that the photo-characteristic seems to bend with a
current saturation for large forward bias. This behaviour, known as rollover effect, was reported by Shen et al. with
ZnO/p-Si junction [35] and others works [36,37]. This current-saturation was ascribed to an additional barrier at the
back contact.

4. Conclusion

We have fabricated ITO/IZO/ZnO/PS/Si(p) and ITO/IZO/PS/Si(p) for photovoltaic conversion. Despite the used
light source was an ordinary tangsten lamp, our structures exhibit a limited photovoltaic effect as solar cell, leading
us to consider them as promising solar cell structures. The structure with an undoped ZnO layer between IZO and
PS layer shows a crossover behaviour of the dark and light J-V curves, which indicates the existence of
recombination at the ZnO/PS interface. Thus, the photo-current is affected. A decay of about 68 % is detected. The
bending and the saturation of the photo-current at high forward bias were attributed to the existence of an additional
barrier at the back contact.

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