Synthesis of yttria-stabilized zirconia lm by Aerosol

Flame Pyrolysis Deposition

Hyunjin You, Kihyun Cho, Yongsub Yoon, Jongmo Im, Dongwook Shin
*
Division of Material Science & Engineering, Hanyang University, 17 Haengdang-dong, Seongdong-gu, Seoul 133-791, Republic of Korea
Received 14 November 2006; accepted 11 July 2007
Available online 19 July 2007
Abstract
In this work, the Aerosol Flame Pyrolysis Deposition (AFPD) technique was applied to deposit yttria-stabilized zirconia powder fromthe liquid
source materials in order to prepare lm type electrolyte for SOFC. The spherical and dense yttria-stabilized zirconia particles were synthesized in
the submicron range and the particle size distribution was dependent on the concentration of the precursor solution and ame conditions. The
spherical and dense solid YSZ particles were synthesized and the XRD results revealed that the crystallinity of particles were already excellent
without additional heat treatment. Mean diameters of the particles were approximately 400600 nm and the particles were polycrystalline
composed of approximately 20-nm-sized grains. YSZ electrolyte thin layer was also fabricated from the liquid source materials by AFPD method.
# 2007 Elsevier B.V. All rights reserved.
Keywords: YSZ; Aerosol Flame Pyrolysis Deposition (AFPD)
1. Introduction
YSZ has various excellent properties as an electrolyte of
SOFC, such as high heat resistance, high mechanical strength,
chemical durability and high ionic conductivity at high
temperature [1,2]. YSZ is more advantageous in terms of high
temperature, mechanical strength and stability compared to
ceria (CeO
2
)-based electrolyte; nevertheless, both are widely
employed as an electrolyte of SOFC. Though ceria-based
electrolyte has a higher ionic conductivity than YSZ, the ionic
conductivity regime of ceria is rather narrow and in reducing
environments, it is partially reduced to allow electronic
conductivity [3].
Various thin lm deposition techniques have already been
applied to YSZ, including chemical vapor deposition (CVD)
[4], sputtering [5], spray pyrolysis [6], electronic spray
deposition (ESD) [7] and ame spray deposition [8]. In this
work, Aerosol Flame Pyrolysis Deposition (AFPD) was used to
prepare yttria-stabilized zirconia on Si-wafer. In this method,
the aerosol generated from liquid type source material by
ultrasonic nebulizer is transported to the high temperature ame
for pyrolysis and intense thermal oxidation takes place within
the ame to produce normally nano-sized oxide particles
in short time. Synthesized nanoparticles are deposited on a
substrate in a form of thin lm and subsequent heat treatment
produces the dense and uniform thin lm by the consolidation
or sintering. The difference of this technique compared to
normal spray pyrolysis is that a high temperature oxy-hydrogen
ame is used for intense reaction within short time. The oxy-
hydrogen ame is very efcient to produce nano-sized particle
since it offers high thermal energy to precursor materials
instantaneously which cannot be easily realized by normal
indirect heating, such as an electric furnace.
In this work, we present the study on the effects of deposition
parameters on the microstructure and the particle size
distribution of YSZ particles synthesized by the Aerosol Flame
Pyrolysis Deposition.
2. Experiments
Schematically shown in Fig. 1 is Aerosol Flame Pyrolysis
Deposition (AFPD) system. The experimental apparatus
consists of an aerosol generator, a deposition chamber and a
gas delivery system. In the AFPD process, a liquid precursor
solution was prepared by dissolving the desired precursors into
a solvent and then atomized into micro-sized droplets by
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J. Anal. Appl. Pyrolysis 81 (2008) 1419
* Corresponding author. Tel.: +82 2 2220 0503; fax: +82 2 2220 4011.
E-mail address: dwshin@hanyang.ac.kr (D. Shin).
0165-2370/$ see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2007.07.002
ultrasonic nebulizer. The aerosol generation was performed by
an ultrasonic nebulizer employing 1.7 MHz resonator, which is
known to generate aerosol of 12 mm diameter.
A precursor solution based on a mixture of zirconium(IV) n-
propoxide Zr(n-C
3
H
7
O)
4
(in n-propanol, 70%, Aldrich) and
yttrium nitrate Y(NO
3
)
3
6H
2
O (99.9%, Aldrich) were used as
precursors and then were ultrasonically agitated in ethanol
(99.9%). Source reagents were dissolved in ethanol and a small
quantity of nitric acid (60%) was added to aid complete
dissolution of these constituents. A Zr/Y ratio of 0.84:0.16 was
chosen with total precursor concentrations (Zr + Y) of 0.1, 0.2
and 0.3 M.
The surface morphology and the cross-section of the
deposited lms were characterized using scanning electron
microscopy (JEOL JSM-5610, JSM-5900LV) equipped with an
Oxford Instruments 6587 Energy Dispersive X-ray Spectro-
meter (EDX). The crystal structure of the deposited lms was
determined by X-ray diffraction (Rigaku (D/max-2500, with
Cu Ka X-ray radiation 40 mA, 100 mV)).
Conductivity was measured by complex impedance method
using Solartron 1260 impedance analyzer and dielectric
interface with an ac voltage of 50 mV amplitude over the
frequency range 1 Hz to 1 MHz at each temperature.
3. Results and discussion
The XRD patterns of the deposited lms are given in Fig. 2
and this result suggests that a fully stabilized cubic phase ZrO
2
was successfully synthesized directly from the liquid precursor
solution. There was no evidence that the amorphous phases
were formed and mixed with the crystalline phase. The
composition of YSZ was Y
0.2
Zr
0.8
O
1.9
when judged based on
the comparison to the data in JCPDS. After sintering, the full
width at half maximum (FWHM) of each peak became
narrower and the peak intensity was increased, which is
ascribed to the enhanced crystallinity. Therefore, it is believed
that the YSZ lm fabricated in this work has very high
crystallinity though the microstructure is slightly inhomoge-
neous due to unsintered white particles.
Fig. 1. A schematic diagram of experimental apparatus of Aerosol Flame Pyrolysis Deposition for the synthesis of YSZ.
Fig. 2. XRD pattern of YSZ powder deposited on Si-wafer substrate. The
comparison of XRD pattern of YSZ measured before and after sintering at
1400 8C for 2 h. YSZ powder was synthesized at H
2
ow rate 2 L/min, O
2
ow
rate 2 L/min, Ar ow rate 1 L/min, turn table temperature at 150 8C, the
concentration of source materials in the precursor solution 0.2 mol%.
Fig. 3. SEM micrograph of YSZ particles synthesized by Aerosol Flame
Pyrolysis Deposition. YSZ powder was synthesized at H
2
ow rate 2 L/min,
O
2
owrate 2 L/min, Ar owrate 1 L/min, turn table temperature at 150 8C, the
concentration of source materials in the precursor solution 0.2 mol%.
H. You et al. / J. Anal. Appl. Pyrolysis 81 (2008) 1419 15
SEM micrographs of the deposited YSZ powders revealed
that the zirconia particles exhibited spherical shape, smooth
surface, submicron size (0.20.6 mm) and extremely low
degree of agglomeration as shown in Fig. 3. No evidence for the
formation of hollow particle was found. The synthesis method
used in this study differs to the previous report [9] in the fuel
type used to supply the heat for thermal reaction. The synthesis
temperature was estimated to 13001800 8C which is greatly
higher than the conventional ame synthesis or spray pyrolysis
process.
Fig. 4 shows the schematics of the mechanism of YSZ
particle formation and SEM images of particles collected at the
various positions in the ame. One can see that the deposition
rate varies position by position, whereas the particle size does
not vary appreciably. The deposition rate tends to increase as
the position moves to the end of the ame.
Fig. 4. The mechanism of particle synthesis by Aerosol Flame Pyrolysis Deposition.
Fig. 5. Cross-sectional SEM image of YSZ lm deposited on Si-wafer (a) before sintering (b) after sintering at 1400 8C for 2 h. YSZ powder was synthesized at H
2
ow rate 2 L/min, O
2
ow rate 2 L/min, Ar ow rate 1 L/min, turn table temperature at 150 8C, the concentration of source materials in the precursor solution
0.2 mol%.
H. You et al. / J. Anal. Appl. Pyrolysis 81 (2008) 1419 16
In general, the particle synthesized by the Aerosol Flame
Pyrolysis has bimodal size distribution [10]. Small particles
are formed a few tens of nanometers in diameter and large
particles are formed generally larger than a few hundreds of
nanometers. The origin of this bimodal distribution is attributed
to two different mechanisms of particle formation. Large
particle is formed by the rapid evaporation of liquid solvent in
high temperature and condensation and precipitation of
dissolved precursors. On the other hand, small particle is
formed by sublimation of precursors or formed ne solid
particle and the formation of plasma due to high temperature of
ame, and subsequent gas phase nucleation and growth. The
nucleation rate will be dependent on the supersaturation of
plasma gas phases and this supersaturation increases at the end
of ame due to reduced temperature. The Brownian coagula-
tion happens during the random ow of solid particles within
the ame and causes the agglomeration of small particles. In
this work, however, the number of small particle seems to be
negligibly small and this experimental observation suggests
that the gas phase nucleation and growth mechanism for small
particle formation is not operating in the synthesis of YSZ.
Since the vapor pressure is low due to its high melting
temperature, it is expected that the supersaturation of zirconia
vapor within ame is not developed enough and the formation
of particle through gas phase nucleation does not proceed
actively.
YSZ was rst deposited on a Si-wafer in the form of porous
soot as shown in Fig. 5(a). The thickness of soot layer was
22 mm and the deposition rate was approximately 1.2 mm/min.
This soot layer shrunk into dense thin lm by the high
temperature sintering at 1400 8C in a furnace as shown in
Fig. 5(b) and the volume shrinkage ratio was approximately 10.
Fig. 6. Deposition rate of YSZ lm as a function of (a) the concentration of
source materials in the precursor solution and (b) the ow rate of H
2
gas.
Fig. 7. SEM micrograph of the YSZ powders synthesized from the precursor solution with the concentration of (a) 0.02 M, (b) 0.1 M, (c) 0.2 M and (d) 0.3 M.
H. You et al. / J. Anal. Appl. Pyrolysis 81 (2008) 1419 17
Fig. 6(a) shows the deposition rate as a function of the
concentration of source materials in the precursor solution. As
expected, the deposition rate increased with increasing
precursor solution concentration due to increased amount of
source materials contained in aerosol droplets. The relatively
low precursor solution concentration is attributed to the loss of
the precursor solution during aerosol transport. The deposition
rate also increased with increasing ow rate of H
2
gas as shown
in Fig. 6(b). The increased deposition rate may be attributed to
the increased ame temperature caused by increased H
2
gas
ow rate and, hence, the increased reaction rates. It was
experimentally conrmed that the ame temperature was
approximately increased by 50 8C as H
2
gas increased by 0.5 L/
min and decreased by 20 8C as O
2
gas decreased by 0.5 L/min.
It was observed that the concentration of precursor solution
had profound effect on particle size and deposition rate, while
the ame temperature affected only the deposition rate. By
comparing the YSZ powders from 0.02, 0.1, 0.2 and 0.3 M
precursor solutions, the average particle size from the 0.02 M
solution is found to be the smallest as shown in Fig. 7(a). The
particle size was gradually increased with increasing concen-
tration of precursor solution. The particle size is largely
dependent on the aerosol size and the concentration of source
liquid as predicted by Lang [11]. Langs equation assumes that
there is no complex aerosol dynamics, such as the breaking up
of large droplets and Brownian coagulations of particles.
Fig. 8 is an example of the impedance spectra of YSZ lm
measuredat various temperatures. The typical spectra, composed
of three semicircles, were observed and each semicircle
components are assigned to grain, grain boundary and the
electrodeelectrolyte interface. The conductivity including grain
and grain boundary components exhibited a typical linear
relationship in Arrehnius type plot as shown in Fig. 9.
Fig. 8. Impedance spectra of YSZ lm measured at various temperatures.
Fig. 9. Conductivity of YSZ as functions of the inverse of temperature.
Fig. 10. The morphology of YSZ lm deposited on Si-wafer after sintering at 1400 8C for 2 h and the EDS spectra of the white and the dark spots. YSZ powder was
synthesized at H
2
owrate 2 L/min, O
2
owrate 2 L/min, Ar owrate 1 L/min, turn table temperature at 150 8C, the concentration of source materials in the precursor
solution 0.2 mol%.
H. You et al. / J. Anal. Appl. Pyrolysis 81 (2008) 1419 18
Fig. 10 shows the image of the surface of YSZ lms sintered
at 1400 8C for 2 h, in which white spherical particles are the
particles not fully sintered. The number density of the white
particle was reduced by increasing the sintering temperature or
sintering time. Though the lm was fully densied, the white
particles were not completely eliminated even after 2 h
sintering probably due to large initial particle size. The dark
portion surrounding white particle is thought to be formed by
material transport during the high temperature sintering and it
lled the pores between original particles in soot lm. The
surface of dense lm was slightly rough since the size of white
particle was comparable to the thickness of dense lm.
Therefore, it is necessary to reduce the soot particle size to
fabricate the completely uniform and smooth lm, though it is
not prerequisite in fuel cell device since the rough surface of
electrode enhances the electrochemical reaction by increasing
the interfacial area. The compositional analysis by energy
dispersive spectroscopy shown in Fig. 5 reveals that the chemical
composition of dark portion is not different from that of white
particle and this result suggests that normal sintering process
occurred. Particle originally formed during the deposition seems
to be porous in nano-scale even though its crystallinity is fairly
good. The porous nature of synthesized particle seems to be
maintained even during the sintering process.
4. Conclusion
Aerosol Flame Pyrolysis Deposition is a versatile and
effective technique to deposit oxide materials. The quality
and properties of the lms depend largely on the process
parameters. The most important parameter is solution
concentration and ame temperature. The precursor solution
is the important parameter, which affects the morphology and
the properties of the deposited lms. The lm morphology and
properties can be drastically changed by using various additives
in the precursor solution.
Aerosol Flame Pyrolysis Deposition technique is regarded
as a strong candidate for the fabrication of thin lm type
electrolyte for SOFC devices and could replace the conven-
tional thin lm deposition techniques, such as sputtering, CVD,
evaporation due to its high deposition rate, simple apparatus.
However, for completely dense lm, the porosity of soot lm
should be low enough and smaller particle size is required. This
is the technical challenge to be attempted in future and authors
are currently seeking the appropriate method to generate the
smaller droplet size.
Acknowledgement
This work was supported by Seoul City, Strategic industry
Innovation Cluster Support Program.
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