Journal of Power Sources 274 (2015) 611e618

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Journal of Power Sources

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Low-temperature performance of yttria-stabilized zirconia prepared

by atomic layer deposition
Dong Young Jang a, Ho Keun Kim a, Jun Woo Kim a, Kiho Bae a, b, Meike V.F. Schlupp c,
Suk Won Park a, Michel Prestat c, Joon Hyung Shim a, *
a
School of Mechanical Engineering, Korea University, Anam-dong, Seongbuk-gu, Seoul 136-713, Republic of Korea
b
High-temperature Energy Materials Research Center, Korea Institute of Science and Technology (KIST), Hawolgok-dong, Seongbuk-gu, Seoul 136-791,
Republic of Korea
c
Nonmetallic Inorganic Materials, ETH Zurich, Wolfgang-Pauli-Str.10, CH-8093 Zurich, Switzerland

h i g h l i g h t s

Conductivity of ALD YSZ is greater than reference YSZ by several orders below 100  C.

Y2O3 concentration of ALD YSZ and humidity are important in electrolyte performance.

SOFCs with ALD YSZ mark OCVs close to 1 V and decent power below 100  C.

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

Article history: We report on the performance of thin-film yttria-stabilized zirconia (YSZ) synthesized by atomic layer
Received 28 August 2014 deposition (ALD) at temperatures of 50e525  C. Electrochemical impedance spectroscopy (EIS) was used
Received in revised form for conductivity measurements. Relatively high conductivity values were observed in the low-
27 September 2014
temperature region when compared to reference values of YSZ synthesized by other methods. To
Accepted 3 October 2014
investigate the conduction mechanism, various experimental variables were modified during the elec-
Available online 16 October 2014
trical measurements, including the ratio of yttria to zirconia in the ALD YSZ films and the atmospheric
conditions. To relate the electrical properties to the structural characteristics, the crystallinity and
Keywords:
Atomic layer deposition
microstructure were investigated using transmission electron microscopy (TEM) and X-ray diffraction
Yttria-stabilized zirconia (XRD). Finally, the suitability of an ALD YSZ membrane as the electrolyte of micro solid oxide fuel cells
Ion conduction was evaluated. An open circuit voltage of almost 1 V and decent power output were successfully
Solid oxide fuel cells measured below 100  C.
© 2014 Published by Elsevier B.V.

1. Introduction the surface-limited, cycle-by-cycle, chemical deposition of nano-

Yttria-stabilized zirconia (YSZ) films have been widely used as
ceramic electrolytes for various high-temperature electrochemical
systems, including solid oxide fuel cells (SOFCs), solid oxide elec-
trolyzers (SOECs), and gas sensors. The main reason for their
widespread use is that YSZ films exhibit reasonably high conduc-
tivity of oxide ions (O2) at elevated temperatures, as well as
excellent thermal, chemical, and mechanical stability. There have
been recent efforts to use atomic layer deposition (ALD) to produce
YSZ electrolytes in order to develop high-performance SOFCs [1e6].
ALD is a modified chemical vapor deposition (CVD) technique for
* Corresponding author. Tel.: þ82 2 3290 3353; fax: þ82 2 926 9290.
E-mail address: shimm@korea.ac.kr (J.H. Shim).
scale films. Using this method, the substrate surface is alternately
exposed to different vaporized source chemicals or precursors.
With each exposure cycle, the film grows until the chemisorbed
precursors occupy the full surface area of the substrate in the form
of a single layer; even with an excessive precursor supply, the
growth will not continue beyond a single layer. For this reason, both
the thickness and the composition of ALD films can be precisely
controlled at the atomic (layer-by-layer) scale [7e11].
ALD-prepared YSZ (hereafter referred to as ALD YSZ) films can
be synthesized by alternating the ALD cycles between the host
material, ZrO2, and the dopant, Y2O3. It is noteworthy that SOFCs
with ALD YSZ electrolytes outperform similar SOFCs using YSZ films
prepared by other thin-film techniques [1,6,12,13]. This enhanced
performance has been attributed to two properties: the reduced
ohmic loss across the ultrathin membrane when used as a

http://dx.doi.org/10.1016/j.jpowsour.2014.10.022
0378-7753/© 2014 Published by Elsevier B.V.
612 D.Y. Jang et al. / Journal of Power Sources 274 (2015) 611e618
freestanding electrolyte in micro-SOFCs, and the greatly improved
surface kinetics of nanocrystalline ALD YSZ films [1,6,12].
Since the activation energy for the migration of O2 ions is
relatively high (0.9e1.0 eV), the ionic conductivity of YSZ tends to
decrease quickly with decreasing temperature [14]. However, no
significant drop in the electrical conductivity has been reported for
YSZ at temperatures below 100  C [15e23]. It has been claimed that
these phenomena are due to either the fast diffusion of protons
(Hþ) through physical pores, or the presence of grain boundaries in
which Hþ seems to reside in the form of hydroxyl ions OH
[3,15,17,18,21e28]. An abundance of Hþ ions and their effect on
conduction during fuel-cell operation have been identified in ALD
YSZ films. These properties are suspected to be a consequence of
sample synthesis using vaporized water as the oxidizing source for
the ALD cation precursors [3,28]. However, to the best of our
knowledge, there are no reports on the electrical properties and
fuel cell performance of ALD YSZ films at temperatures below
100  C, where proton diffusion is dominant.
In this work, we prepared nanoscale YSZ thin films by ALD and
measured the conductivity across the films at temperatures as low
as 50  C. The properties of the ALD films were evaluated in relation
to the concentration of Y2O3. Our results were compared with
reference data for similarly thick YSZ thin films, fabricated by other
techniques, including spray-pyrolysis (SP) and aerosol-assisted
CVD (AA-CVD). Finally, we tested the applicability of ALD YSZ
membranes as freestanding electrolytes in dry hydrogen micro-
SOFCs. The fuel-cell performance was evaluated in terms of
voltage and current.
2. Experimental
Tetrakis(ethylmethylamido) zirconium(IV) (UP Chem.) and
tris(methyl-cyclopentadienyl) yttrium(III) (Strem Chem.) were
used as cation precursors for the ALD of ZrO2 and Y2O3, respectively,
and distilled water was used as the oxidant. The temperature of
deposition was 250  C, and dry nitrogen was used as the purge and
carrier gas (flow rate of 0.5 sccm). The precursor and oxidant
pulsing times were both 0.5 s, followed by 30 s of N2 purging. The
ALD cycle ratios of ZrO2 to Y2O3 were 2:1, 4:1, and 10:1, resulting in
about 15e16, 8e9, and 2e3 mol% of Y2O3, respectively [4,16,17].
This was confirmed by X-ray photoelectron spectroscopy (XPS, SSI
S-Probe, monochromatic Al Ka radiation). For comparison, pure
ALD ZrO2 films were also prepared.
The ALD YSZ films were deposited onto dense Pt-coated Si(001)
wafers with a titanium interlayer for PteSi binding. This underlying
Pt/Ti layer was fabricated with a 200 W Hitachi E-1030 DC sput-
terer. The underlying Pt/Ti layer acted as the bottom electrode for
the cross-plane conductivity measurements. The sputtering was
conducted in an Ar environment at a pressure of 1 Pa, and the
Fig. 1. (a) Experimental setup for cross-plane impedance measurements of the ALD YSZ films. (b) HRTEM image of 180 nm thick ALD YSZ (4:1) film, fabricated between sputtered Pt
electrodes. (c) XRD patterns of 200 nm thick ALD YSZ (4:1) films, fabricated on bare-Si(001) and Pt/Ti-coated Si(001) wafers.
thickness of the layer was approximately 150 nm. The top elec-
trodes were sputtered onto the ALD YSZ films using shadow masks
to form circular patterns of dense, 250 nm thick Pt layers. The
diameter of the top electrodes varied from 0.5 to 2 mm, as shown in
Fig. 1(a). The variation of electrode size was used to confirm the
origin of the measured impedance (i.e., that it originates across the
electrolyte membrane between electrodes).
The thickness and microstructure of the films were evaluated
using transmission electron microscopy (TEM, JEOL JEM 2100F) in
high-resolution (HR) and high-angle annular dark-field (HAADF)
scanning modes. The crystal structures of the ALD YSZ samples
were obtained by X-ray diffraction (XRD, TTK 450). The samples
were heated in ambient air (relative humidity (RH) of 50%) or dry
air to between 50 and 525  C, and analyzed with electrochemical
impedance spectroscopy (EIS, Gamry Reference 3000 Potentiostat/
Galvanostat/ZRA). Before the electrical measurements, the sample
temperatures were monitored using a separate temperature probe
attached to the surface of a blank substrate for temperature cali-
bration. Data analysis and fitting were performed using commercial
circuit-fitting software (Gamry PHE200).
For the fabrication of micro-SOFCs with freestanding ALD YSZ
electrolytes, micro-patterned Si3N4/Si wafers were prepared with
a process similar to that reported previously in the literature
[1,3,6]. The area of the freestanding Si3N4 window was
180 mm  180 mm, which represents the working area of the
micro-SOFCs. A 100-nm thick ALD YSZ layer was deposited on top
of the Si3N4 side. For comparison, a 100-nm thick YSZ layer was
produced by pulsed laser deposition (PLD). A KrF excimer laser
(l ¼ 238 nm, Compex Pro 201F, Coherent) with a laser fluence of
~2.5 J cm2 was used for target ablation. During PLD, the substrate
temperature and ambient O2 pressure were maintained at 700  C
and 6.67 Pa, respectively. After the preparation of YSZ films by ALD
and PLD, reactive-ion etching (RIE, CF4 etching gas) was performed
to remove the backside Si3N4 membrane. A 100-nm thick, porous
Pt layer was deposited on both sides of the wafer with DC sput-
tering; these layers acted as the catalytic electrodes of the micro-
SOFCs. The measured sputtering growth rate was 0.02 nm s1 at
350 W and an Ar environment pressure of 12 Pa. A TEM cross-
sectional image of the resulting membrane-electrode assembly
(MEA) is shown in Fig. 1(b). The performance of the micro-SOFCs
was evaluated using the setup described in our previous report
[32]. Dry H2 gas passed through water at a constant temperature
in a thermostat bath, resulting in 3%PH2O. The humidified H2 was
fed into the anode-side compartment while the cathode side was
exposed to ambient air during the measurements. The open circuit
voltage (OCV) was monitored from 25  C to 100  C with constant
temperature increments over time (0.125  C s1). Currentevoltage
(IeV) plots were recorded from the micro-SOFCs at 100, 200, 300,
and 400  C.
 D.Y. Jang et al. / Journal of Power Sources 274 (2015) 611e618
3. Results and discussion
3.1. Microstructure of ALD YSZ films
The microstructure of the ALD YSZ samples was analyzed using
HRTEM. A total of 1450 ALD cycles were run, and thicknesses of 177,
158, 180, and 193 nm were achieved for the ALD ZrO2, ALD YSZ
(2:1), ALD YSZ (4:1), and ALD YSZ (10:1) films, respectively. This
implies that the growth rate was approximately 1.22, 1.09, 1.24, and
1.33 Å/cycle, respectively. We suspect that the differences in growth
per cycle arise from differences in the ALD nucleation modes of
ZrO2 and Y2O3 for different surfaces. A similar trend was observed
in a previous report on ALD YSZ films [29]. We confirmed that all
films grew in the form of crystalline columnar grains, which agrees
with previous results from samples prepared under the same ALD
conditions [28,30,31]. Fig. 1(b) shows a representative TEM cross-
section image of the ALD YSZ (4:1) sample and Fig. 1(c) presents
the corresponding XRD patterns for the 4:1 film deposited on Pt/Ti-
coated and bare single crystal Si(001) wafers. It is interesting to
note that the grain columns did not grow completely perpendicular
to the substrate, as shown in Fig. 1(b), presumably because they
were grown on polycrystalline Pt. This finding is supported by a
comparison with the microstructure of ALD YSZ films deposited on
a different surface, as described in our previous study [30]. The XRD
patterns shown in Fig. 1(c) confirm the presence of polycrystalline
cubic features, even in case of the ALD YSZ films deposited on top of
a Pt electrode. The 2q values of the crystalline peaks of our films
matched the reference peaks of the cubic phase of YSZ.
Enlarged HRTEM images of the prepared ALD ZrO2, ALD YSZ
(2:1), ALD YSZ (4:1), and ALD YSZ (10:1) samples are presented in
Fig. 2(a)e(d), respectively. The images show that the films grew
into a fully crystalline state. Fig. 2(e)e(h) show the corresponding
diffraction patterns of the samples. The presence of cubic YSZ seen
in the XRD data was confirmed by the diffraction pattern for all
stoichiometric ratios of the YSZ samples. For cubic crystals with
lattice constant a, the spacing between adjacent lattice planes, d,
can be calculated with Equation (1):
Fig. 2. HRTEM images (upper row) and corresponding diffraction patterns (lower row) of (a) & (e) ALD ZrO2, (b) & (f) ALD YSZ (2:1), (c) & (g) ALD YSZ (4:1), and (d) & (h) ALD YSZ
(10:1) films. Inset tables in (e)e(h) give the d-spacing values measured from the diffraction images and (g) compared with the calculated value using the cubic YSZ lattice constant
(a ¼ 5.139 Å).
613
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
a2
d¼ (1)
h þ k2 þ l2
2
where (h k l) represents the plane normal to the (h, k, l) direction. As
shown in the inset tables of Fig. 2(f)e(h), the d values measured
correspond to those calculated from the cubic YSZ lattice param-
eter. This indicates that the ALD YSZ films grew in the cubic phase,
regardless of the dopant concentration. This agrees with previous
observations on ALD YSZ films with various dopant concentrations
[28,31]. In contrast, the ALD ZrO2 film shows reflections that do not
match the d values of cubic zirconia, as shown in Fig. 2(e).
The HAADF-scanning TEM (STEM) cross-sectional images
shown in Fig. 3 confirm the presence of 1e5 nm pores inside the
grains, and that this porosity is distributed evenly throughout the
YSZ film. The size of the pores was relatively large in the ALD YSZ
(4:1) and (2:1) films in which the concentration of Y2O3 is high.
3.2. Electrical characterization of ALD YSZ (4:1) film
We first examined the electrical properties of the ALD YSZ (4:1)
sample, which showed a composition close to 8 mol% of Y2O3. The
cross-plane impedance of this sample was analyzed using EIS by
sweeping the frequency of the input AC signal from 1 MHz to 0.1 Hz
while keeping the oscillation amplitude constant at 10 mV. Fig. 4
shows representative spectra measured from the ALD YSZ (4:1)
sample. For temperatures below 350  C, the resulting Nyquist plots
show a single depressed semicircle. To confirm that the width of the
semicircle truly represents the electrolyte impedance, bias voltages
of 0, 0.5, and 0.7 V were applied during the impedance measure-
ments. This method was previously shown to successfully separate
the impedance of electrode processes from that of electrolyte
processes [12,31e33]. No significant changes in the shape or
magnitude of the semicircle were identified under varying bias
conditions, as shown in Fig. 4(c). Therefore, it can be concluded that
the impedance originates from the electrolyte process. For tem-
peratures above 350  C, two distinguishable arcs appear in all
614 D.Y. Jang et al. / Journal of Power Sources 274 (2015) 611e618

Fig. 3. HAADF-STEM cross-sectional images of (a) ALD ZrO2, (b) ALD YSZ (10:1), (c) ALD YSZ (4:1), and (d) ALD YSZ (2:1).

Fig. 4. Nyquist impedance plots of the ALD YSZ (4:1) sample, measured on an electrode area of 0.5 cm in diameter for temperatures ranging from 50 to 400  C and frequencies from
1 MHz to 0.1 Hz. The red curves are the fitted results with the equivalent circuit models given in the insets. (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.)
 D.Y. Jang et al. / Journal of Power Sources 274 (2015) 611e618
impedance measurements, as shown in Fig. 4(d). The spectra for
frequencies below 4000 Hz changed according to the applied bias
conditions, suggesting that the left-hand semicircle, which
appeared at higher frequencies, was a true representation of the
electrolyte impedance. It is interesting to note that there was no
separation of the grain and grain-boundary contributions to the
impedance spectrum. We suspect that this is a result of the cross-
plane measurements being taken across the ALD YSZ columns,
which offers little possibility of measuring the conduction through
intergranular regions or across grain boundaries. This explanation
is supported by previous studies on nanogranular YSZ, measured in
a similar temperature regime [19,20].
The electrolyte impedance spectra were fitted with equivalent
circuits. They consist of a simple resistor connected in series with
one pair (2 resistors) or two pairs (4 resistors) of resistors and a
capacitive constant-phase element (CPE or Q) connected in parallel,
as illustrated in Fig. 4(a)e(d). The resistors in this equivalent circuit
represent the impedance from other sources, including the resis-
tance of the electrode contact and the device wires, both of which
are irrelevant to the electrolyte or electrode processes. The capac-
itance, which represents the electrolyte process, can be calculated
from the Q-fitting values using Equation (2):
 1=n
C ¼ R1n Q (2)
where n is the so-called “nonideality parameter” [34]. As a result,
the capacitance values from the semicircles below 350  C or the
high-frequency arcs above 350  C were calculated to be
107e106 F cm2. This corresponds to the reference capacity value
of bulk YSZ containing 8 mol% of Y2O3 [35], whereas the low-
frequency arcs that appeared above 350  C showed capacitance
values 1e2 orders of magnitude larger, as shown in Fig. 5. This also
confirms that the single semicircles or the left-hand high-fre-
quency spectra with two semicircles of the Nyquist plots represent
the electrolyte impedance.
We converted the electrolyte impedance of the films to con-
ductivity values using Equation (3):
sALD YSZ ¼ ðRALD YSZ Þ1 $tALD YSZ =Aelectrode (3)
Fig. 5. Comparison of the area-specific capacitances, calculated from the fits of the
Nyquist impedance plots. The ALD YSZ (4:1) films were measured at temperatures of
50e525  C.
615
where sALD YSZ is the electrical conductivity of the sample, RALD YSZ
the impedance of the electrolyte part of the sample, tALD YSZ the
thickness, and Aelectrode the area of the top electrode. The resulting
Arrhenius plots of the ionic conductivity of the ALD YSZ (4:1) films
are shown in Fig. 6. Three ALD YSZ (4:1) samples produced under
the same experimental conditions were evaluated over different
temperature ranges. The first sample was measured at 80e450  C;
the second at 50e225  C; and the third at 350e525  C. The simi-
larity of the resulting data in the overlapping temperature ranges
(except for a few low-temperature data points) indicates that our
measurements are highly reproducible.
At elevated temperatures (T > 350  C), the measured conduc-
tivity matches the reference values of YSZ, implying that the oxide
ion conduction dominates in this case [36,37]. This high-
temperature electrical conductivity has also been reported in
numerous publications for both dense and porous YSZ films
[18e23].
Below 100  C, the conductivity increased with decreasing tem-
perature without thermal activation if measured in normal ambient
air. This peculiar low-temperature trend has been reported several
times [18e23] but its origin is yet unknown. The proposed expla-
nations so far involve different mechanisms: Chiodelli et al., Kim
et al., and Avila-Paredes et al. have claimed that proton diffusion
along grain boundaries accounts for this enhanced conductivity in
dense nanogranular YSZ film [18e21]. On the other hand, Scherrer
et al. and Schlupp et al. concluded that there is no proton con-
duction through grain boundaries if the YSZ film is dense and that
conduction of protons occurs only in internal pores wherein
physisorbed or chemisorbed water is present [22,23]. As observed
in our HAADF-STEM images, the present ALD YSZ films consist of
columnar grains with intragranular pores, as shown in Figs. 2 and 3.
Based on this structure, we speculate that proton conduction along
the surface of grains and across intragranular space is the most
appropriate mechanism to account for our results. This observation
is also supported by previous experiments using ALD that identified
high concentrations of 2Hþ ions, the heavy hydrogen isotope,
incorporated in the nanogranular YSZ film if the membrane was
either exposed to 2H2O or synthesized in an environment con-
taining 2H2O [3,28]. At temperatures of 100e300  C under normal
atmospheric conditions, the conductivity of the ALD YSZ films
Fig. 6. Conductivity of ALD YSZ (4:1) films measured at temperatures ranging from 50
to 525  C under normal atmospheric conditions (RH ~ 50%). Reference data of YSZ
synthesized by other methods are shown for comparison [22,23,36,37].
616 D.Y. Jang et al. / Journal of Power Sources 274 (2015) 611e618
showed Arrhenius behavior. The activation energy for the increase
in conductivity with increasing temperature in this temperature
range was determined to be relatively low (0.16 eV). In comparison,
the conductivity of the ALD YSZ (4:1) film measured in dry air
significantly decreased by 1e2 orders of magnitude, as shown in
Fig. 7. This strongly suggests that the ALD YSZ films conduct protons
along water or hydroxyl channels in the relatively low-temperature
regime. The conductivity could not be measured below 120  C
under dry conditions because on further dehydration of the
membrane, the impedance increased beyond the measurement
range of the device.
It should be noted that at relatively low temperatures
(50e160  C), the ALD YSZ (4:1) sample exhibited the highest con-
ductivity of all investigated ALD YSZ samples. The conductivity was
particularly large in comparison to that of YSZ synthesized by other
techniques, such as nanopowder sintering, AACVD, and SP, as
shown in Fig. 6 [18e23,36,37]. The specific characteristics of the
film fabrication techniquedthe ALD YSZ films were synthesized
using water vapor as the oxidizing agent at a relatively low tem-
perature (250  C)dmay have provided more favorable conditions
for water to be adsorbed onto the material surface. Our previous
works discussed the effect of the synthesis conditions on the for-
mation of hydroxyl ions and proton conduction in ALD YSZ films
[3,28]. We argue that the ALD process results in a dramatic increase
in the ionic conductivity compared to YSZ films fabricated by other
methods in the medium temperature regime.
3.3. Electrical characterization of ALD YSZ (10:1) and ALD ZrO2
films
We measured the conductivity of the ALD YSZ (10:1) and ALD
ZrO2 films in the same manner as that of the ALD YSZ (4:1) sample.
As a result, we confirmed that the conductivity dramatically
decreased as the concentration of Y2O3 decreased, as shown in
Fig. 7. It has been widely reported that the introduction of Y2O3 into
a ZrO2 host lattice creates oxide-ion vacancies for charge neutrality
and that water tends to be chemisorbed at such vacancy sites,
which dissociates into hydroxyl (OH) groups [15,38e40]. This
process can be expressed by the following Kro €gereVink notation:
Fig. 7. Conductivity of ALD YSZ (4:1) films measured at temperatures ranging from 50
to 250  C under normal atmospheric (RH ~50%) and dry-air conditions in comparison
with the conductivities of ALD YSZ (10:1) and ALD ZrO2 films in ambient air.
     
H2 OðgÞ þ V∙∙ X
O YSZ þ OO 4 2ðOHÞ∙O YSZ (4)
YSZ
where V∙∙ X
O denotes an oxide-ion vacancy, OO neutral oxygen, and
∙
ðOHÞO the protonic defect associated with lattice oxygen. Our ex-
periments using heavy water 2H2O as the oxidant in the ALD of YSZ
and secondary-ion mass spectrometry (SIMS) measurements
clearly confirmed that the concentration of OH groups was line-
arly related to the concentration of the dopant cations (Y3þ) [28].
This observation provides evidence that the conduction of protons
via OH ions formed by oxygen vacancies along the surfaces of
pores, as observed in the HAADF-STEM analysis (Fig. 3), dominates
the overall conduction of the present ALD YSZ samples [40,41].
Moreover, we found that the impedance of the ALD YSZ (2:1) film
was too high to determine its conductivity and suspect that this is
because the concentration of Y2O3 is too high to be completely
doped into the ZrO2 lattice. Our previous SIMS experiments also
confirmed that the concentration of Hþ or OH in ALD YSZ (2:1) is
lower than in ALD YSZ (4:1) [28]. Therefore, the presence of oxygen
vacancies where hydroxyl groups or proton conduction channels
could form has not been explicitly confirmed in this sample.
3.4. Fuel-cell performance of ALD YSZ (4:1) at low temperatures
Fig. 8(a) shows that the micro-SOFC with a 100-nm thick ALD
YSZ membrane (ALD-SOFC) exhibits an OCV of more than 0.8 V at
60  C, while the OCV of the cell with PLD YSZ (PLD-SOFC) is un-
stable until 100  C. The ALD-SOFC shows a stable OCV close to 1 V
over 100e400  C, as shown in Fig. 8(c). The IV curve of this ALD-
SOFC was successfully measured at 100  C, implying that the ALD
YSZ membrane is electrochemically active as an electrolyte even at
such a low temperature, as shown in Fig. 8(b). In contrast, PLD-SOFC
failed to produce power even up to 200  C. It can be confirmed that
ALD YSZ and PLD YSZ hold similar nanogranular structures, as re-
ported several times in the literature [3,6,22,23]. Therefore, the
unique characteristic of the ALD process, in which the film was
synthesized under humid conditions causing a significant amount
of protons or OH ions to be incorporated into the membrane [28],
is responsible for the enhanced ion conduction and good perfor-
mance of the fuel cell at low temperatures, compared to nano-YSZ
synthesized by other techniques. It is noteworthy that the power
was enhanced exponentially with increasing temperature, as
shown in Fig. 8(c), even though the conductivity of ALD YSZ at
100  C was already as high as at 300  C, as identified from the cross-
plane conductivity measurements shown in Fig. 6. This implies that
the overall fuel-cell performance is governed by charge-transfer
reactions at the electrodeeelectrolyte interface rather than by
charge transport through the membrane.
4. Conclusions
In this work, ALD YSZ films with various concentrations of Y2O3
were evaluated in terms of their microstructure by TEM/XRD,
conductivity by cross-plane impedance measurements at temper-
atures ranging from 50 to 525  C, and fuel-cell performance if used
as an electrolyte membrane. Regardless of the Y2O3 content, a fully
crystalline structure was identified from the HRTEM measure-
ments. Intragranular pores 1e5 nm in size were observed at high
magnification (HAADF-STEM images). The pore size was relatively
large in case of the ALD YSZ (4:1) and (2:1) samples with a high
concentration of Y2O3. Under normal atmospheric conditions
(including humidity), the conductivity of the ALD YSZ (4:1) sample
was found to be significantly greater than that of the reference YSZ
film with 8 mol% of Y2O3 below 300  C. In contrast, the conductivity
 D.Y. Jang et al. / Journal of Power Sources 274 (2015) 611e618 617

Fig. 8. (a) OCV of SOFCs with ALD YSZ and PLD YSZ electrolytes at 25e100  C. (b) Fuel-cell performance of SOFC with ALD YSZ electrolyte at 100  C. (c) OCV and maximum power
density of SOFC with ALD YSZ electrolyte at 100, 200, 300, and 400  C. (d) Cross-sectional image of the micro-SOFC with 100-nm thick ALD YSZ electrolyte.

dropped by 1e2 orders of magnitude when measured under dry MEMS micro electro-mechanical systems
conditions. This is attributed to the proton-conduction mechanism CVD chemical vapor deposition
via water or hydrated groups along the surface of intragranular SP spray-pyrolysis
pores below 300  C, and via oxygen vacancies above 350  C. As the AA-CVD aerosol-assisted CVD
concentration of the Y2O3 dopant decreased in the ALD YSZ films, XPS X-ray photoelectron spectroscopy
the conductivity dramatically decreased. This suggests that oxygen Pt/Ti dense Pt for bottom electrodes/Ti adhesion layer between
vacancies are introduced by the doping of Y2O3 into ZrO2, which in Pt and Si wafer
turn form hydroxyl channels along the pore surface for proton HR high resolution
conduction. The conductivity of the ALD YSZ (4:1) film was several HAADF high-angle annular dark-field
orders of magnitude greater than that of reference YSZ films with RH relative humidity
8 mol% of Y2O3 that were synthesized on a similar scale but by PLD pulsed laser deposition
different methods (at 50e160  C). SOFCs with an ALD YSZ elec- RIE reactive ion etching
trolyte showed satisfactory fuel-cell performance with an OCV near MEA membrane electrode assembly
1 V at 100  C; no stable OCV could be measured from cells with a OCV open circuit voltage
PLD YSZ electrolyte, even at temperatures up to 200  C, regardless IV current voltage
of the similar nanograin structure of both materials. We suspect HRTEM high-resolution TEM
that the intrinsic characteristics of the ALD process in which the STEM scanning TEM
films were fabricated using water vapor at a relatively low tem- CPE constant phase element
perature (250  C) contributed to the enhanced conduction and fuel ALD SOFC micro SOFC with 100 nm thick ALD YSZ membrane
cell performance. PLD SOFC cell with PLD YSZ

Acknowledgments
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