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Surface & Coatings Technology 202 (2007) 1226 1230

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Deposit of dense YSZ electrolyte and porous NiOYSZ anode for SOFC
device by a low pressure plasma process
F. Rousseau, S. Awamat, M. Nikravech, D. Morvan , J. Amouroux
Laboratoire de Gnie des Procds Plasmas et Traitements de Surface, ENSCP - Universit Pierre et Marie Curie,
11 rue Pierre et Marie Curie, 75005 Paris, France
Available online 15 August 2007

Abstract
A low pressure plasma process was used in the laboratory to synthesize very pure Sr-doped LaMnO3 porous layers, which could be used as a
SOFC cathode. Recent experimental work allowed to adapt the process to synthesize both the YSZ dense electrolyte and the NiOYSZ porous
anode in one step. The raw material was a mixture of Y and ZrO nitrates dissolved in water. Nitrates were introduced in the argon/oxygen plasma
discharge in order to obtain on a quartz substrate a very pure YSZ layer at low temperature (T 360 K). After depositing YSZ as a layer, Ni
nitrates were progressively added to the mixture of Y and ZrO nitrates in order to obtain a NiOYSZ layer presenting concentration gradients.
SEM-EDX analyses were performed on the fractured cross section of the YSZ/NiOYSZ/NiO stack. Micrographs showed that the YSZ layer is
dense, contrary to the porous NiOYSZ and NiO ones. EDX analyses confirmed the purity and the composition of the YSZ layer. The presence of
concentration gradients of Ni and YSZ along the cross section was demonstrated: contrary to the YSZ concentration, the Ni one increases from the
YSZ layer up to the surface. No Y and Zr elements were detected at the surface of the YSZ/NiOYSZ/NiO stack.
2007 Elsevier B.V. All rights reserved.
Keywords: Cold plasma process; SOFC; Low pressure plasma; NioYSZ layer; Gradient of concentration

1. Introduction
Solid Oxide Fuel Cells (SOFCs) continue to be explored as a
potential power generator for the future [1]. An SOFC usually
consists of a LaxSrx(Mn,Co)O3 cathode, a ZrO2Y2O3 (Yttria
Stabilised Zirconia) electrolyte and a NiNiO anode [24].
Because of the high operating temperature, the use of methane
can be considered at the anode. The internal stream reforming
results in a simpler and cheaper device owing to the exclusion of
a pre-reformer [5]. Deposition techniques such as calcinations
[4], solgel method [6] or spray pyrolysis [7] are used for the
synthesis of SOFC materials. However, if they are usual ways to
synthesize ceramic, they often take a long time as they require a
high number of steps [48]. Moreover, the deposited coatings
may contain pollutants because of the chemical species which
are used during the synthesis.
The chemical reactivity, ionic or electrical conductivity of
SOFC layers depend on their structure, purity and composition,
Corresponding author. Tel.: +33 146334283; fax: +33 146335813.
E-mail address: daniel-morvan@enscp.fr (D. Morvan).
0257-8972/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2007.07.089

which are functions of the manufacturing process parameters. In

the case of an NiYSZ anode, the synthesis path, the composition
as well as the microstructure of the layer affect the deposition of
carbon at the surface [5]. To improve the quality of the deposits
and to reduce the production costs by integrating the depositing
steps into a single process, new production techniques such as
Electrophoretic Deposition (EPD) [9], Electron Beam-Physical
Vapor Deposition (EB-PVD) [10] or plasma spray processes
[11,12] are being developed.
In order to produce a SOFC high quality cathode, a low
pressure plasma process has been developed in the laboratory
[1317]. The raw material (lanthanum nitrates, strontium nitrates, manganese nitrates or cobalt nitrates) was injected into
the plasma reactor to obtain a porous La1 xSrx(Mn,Co)O3 layer
on YSZ pellets (20 or 25 mm in diameter) (Fig. 1). Recent
experimental work proved that the SOFC cathode deposited in
the low pressure plasma reactor has a high electronic conductivity and a good catalytic activity, which allows the reduction of O2 into O2[18].
The properties of the low pressure plasma process were used
to investigate the synthesis of the dense YSZ, porous NiOYSZ

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Fig. 1. Surface of a LaMnO3 layer deposited in YSZ substrate.

and NiO layers. The structure of YSZ and NiO was studied by
X-ray diffraction (XRD). Scanning Electron Microscopy with
Energy Dispersive X-ray facility (EDX) enabled to study the
surface and the cross section of the layers. The composition of
the coatings was investigated by EDX analyses.
2. Description of the low pressure plasma process
The low pressure plasma process is described in Fig. 2. The
plasma reactor consists of a Pyrex tube (560 mm in length and
50 mm in diameter) equipped with a convergent nozzle (3, 5 or
7 mm in diameter). Mass flow meters enabled to control the
composition, the flow and the pressure of the plasma gases. The
plasma gases were a mixture of Ar and O2 in various ratio
(maximum flow 1.66 cm3 mn 1, usual ratio 50% O2 50% Ar).
A vacuum pump equipped with dust and acid filters allowed to
maintain the pressure within a range of 250400 Pa (at the exit
of the reactor). A 40 MHz RF generator was used to initialise

Fig. 3. Injection system developed for the deposition of YSZ and NiOYSZ
layers.

and maintain the plasma discharge by means of inductive coils

located on the nozzle with an available power of 50500 W in
the reactor.
The low pressure plasma process is flexible because the raw
material is dissolved in a solution. Most of the atomic elements
can be found dissolved into a solution as ICP-DCP standard
solution appellation (1000 or 10000 ppm, Sigma Aldrich, Alfa
Aesar). In the case of the La1 xSrx(Mn, Co)O3 deposits, the
raw material was a mixture of lanthanum nitrates, strontium
nitrates, manganese nitrates or cobalt nitrates [1317]. The
composition of the mixture was calculated according to the
composition needed for a La1 xSrx(Mn, Co)O3 layer. The raw
material was introduced through the plasma reactor by means of

Fig. 2. Plasma process experimental set-up.

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F. Rousseau et al. / Surface & Coatings Technology 202 (2007) 12261230

Fig. 4. XRD patterns of YSZ deposited on NiO substrate (annealed at 750 C for
1 h).

an injection system. An ultrasonic sprayer enabled to produce

micrometric droplets of water containing nitrates. Pressure
differed between the sprayer and the reactor (from 4 104 down
to 300 Pa), which led to injecting precursors through the plasma
discharge. Some recent experimental work proved the role of
oxidant species (O from the dissociation of O2 and OH from
the decomposition of water) on the oxidization of nitrates
[16,17]. When the micrometric droplets went through the
plasma, the water vaporised and the nitrates reacted with O and
OH to form LaO, SrO, MnO or CoO bond. Finally, particles
were left to form a La1 xSrx(Mn, Co)O3 deposit on a YSZ
substrate, which grew into a layer 0.6 m mn 1 thick. Because
the ICP-DCP solutions had a high purity, no pollutants were
found in the coatings [1317].
The oxidant properties of the Ar/O2/H2O plasma were used
to synthesize and deposit YSZ, NiOYSZ and NiO layers on a
quartz substrate. The raw material was a mixture of ZrO nitrates,
yttrium nitrates and Ni nitrates (Sigma Aldrich). A new injection system was tested in order to increase the deposition rate
(Fig. 3). The system consisted of a capillary which was coupled
with a switch (200 m in diameter). The capillary was used to
suck up the solution of nitrates precursors. The difference in
pressure between the outside (1 105 Pa) and the inside of the
reactor (300 Pa) allowed to inject nitrates into the plasma reactor

Fig. 5. XRD patterns of NiO deposited on quartz substrate (annealed at 750 C

for 1 h).

Fig. 6. Micrograph showing the surface of YSZ/YSZNiO.

(power = 280 W). The system enabled to deposit YSZ/YSZ

NiO/NiO up into a coating 1 m mn 1 thick.
3. Deposition of YSZ, NiOYSZ and NiO layers
ZrO nitrates and yttrium nitrates were injected first to deposit
a thin 10% YSZ layer on quartz pellets. Ni nitrates were then
progressively added to the mixture of Y and ZrO nitrates to
decrease the concentration of Y and Zr and increase the concentration of Ni. The aim was to deposit a NiOYSZ coating
presenting gradients of concentration.
During the deposition of YSZ, a white homogenous layer
became visible on the quartz substrate. After the deposition of
NiOYSZ on YSZ, a black coating was obtained in the plasma
reactor. The multi-layer was annealed at 750 C for one hour to
complete the oxidisation of the residual nitrates. Scratching tests
with a scalpel proved that the layer strongly adhered to the
quartz substrate.
In some previous experimental work, YSZ layers deposited
on NiO pellets and NiO coatings deposited on quartz substrates
were analysed by XRD (Figs. 4 and 5). The XRD patterns

Fig. 7. Fractured cross section of YSZ/YSZNiO observed by SEM.

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Fig. 8. EDX analyses performed on the cross section of YSZ/YSZNiO.

showed that both the YSZ and NiO deposited in the plasma
reactor exhibited a crystalline structure in accordance with the
product needed.
The surface and the fractured cross section of the YSZ/YSZ
NiO/NiO multi-layer was observed by SEM as shown in Figs. 6
and 7. The micrograph in Fig. 6 shows that the surface of the
NiO layer is porous and made up of agglomerated particles. The
YSZ layer deposited on the quartz substrate is dense, contrary to
the NiOYSZ and NiO layers which are porous (Fig. 7). The
porosity observed at the surface is seen to extend throughout the
bulk of the NiOYSZ coating. The Visilog software was used to
estimate the porosity of the NiOYSZ and NiO layers. Porosity
was calculated to be 25% 5%.
The EDX analyses performed on the YSZ (A), NiOYSZ
(B) and NiO (C) layers are shown in the Fig. 7. The results are
summed up in Fig. 8. No undesirable elements were detected in
the YSZ layer (Zr = 78.65 at.% and Y = 21.35 at.%). Such elements as Zr, Y and Ni were detected in the NiOYSZ layer (B).
Results confirmed that the addition of Ni nitrates into the
mixture of ZrO nitrates and Y nitrates during the deposition
allowed to obtained a multi-compound layer. An EDX performed at the surface of the multi-layer (C) detected only Ni
elements. No Zirconium or Yttrium was found, which proved
that the addition of Ni nitrates progressively decreases the
concentration of Zr and Y in the raw material.
The EDX confirmed that the plasma reactor enabled to
synthesise and deposit a YSZ/YSZNiO/NiO multi-layer in one
step. The concentrations of Zr and Y decrease while the concentration of Ni increases from the substrate to the surface. The
gradients of concentration should improve the chemical, mechanical and thermal compatibility of the SOFC layers.
4. Conclusion
A YSZ/YSZNiO/NiO multi-layer was deposited in one step
through a low pressure plasma process. XRD patterns confirmed that the YSZ and NiO deposited in the plasma reactor

and annealed at 750 C for one hour exhibit a crystalline

structure. The observation by SEM showed that the YSZ layer is
dense contrary to the NiOYSZ and NiO coatings which are
porous. EDX analyses confirmed that the concentrations of Zr
and Y decrease while the concentration of Ni increases from the
YSZ to the layer's surface. EDX analysis did not detect undesirable elements, which proves that the deposited layer is of a
high degree of purity. Further experimental work will consist in
exploring the electrical and electrochemical properties of the
YSZ/YSZNiO/NiO multi-layer.
The flexibility of the low pressure plasma process will
allow to investigate the one step synthesis and deposit of a
LaxSrx(Mn, Co)O3/LaxSrx(Mn, Co)O3YSZ/YSZ/YSZNiO/
NiO multi-layer. A multi-layer presenting gradients of concentration should increase the thermal, chemical and mechanical
stability of the SOFC stack.
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