Synthesis and hydrogen gas sensing properties of ZnO wirelike thin films

Nguyen Le Hung, Eunseong Ahn, Seongyong Park, Hooncheol Jung, Hyojin Kim,a
Soon-Ku Hong, and Dojin Kim
Department of Materials Science and Engineering, Chungnam National University, Daeduk Science Town,
Daejeon 305-764, Republic of Korea
Chanyong Hwang
Advanced Industrial Technology Group, Division of Advanced Technology, Korea Research Institute
of Standards and Science, Daejeon 305-600, Republic of Korea
Received 15 June 2009; accepted 14 September 2009; published 28 October 2009
The authors investigated the hydrogen gas sensing properties of the ZnO wirelike films synthesized
by two consecutive steps: thermal oxidation of sputtered Zn metallic films in dry air. Structural
characterization revealed that the authors synthesized polycrystalline wurtzite ZnO films of a
wirelike structure with a width of less than 100 nm and a length of several micrometers, possibly
consisting of a chain of ZnO nanocrystallites with a mean granular size of 15 nm. It was found from
the gas sensing measurements that the ZnO wirelike films exhibited a maximum sensitivity, defined
as a ratio of the change in conductance upon exposure to H2 gas in dry air over the conductance in
dry air, G / Ga, of 283% to 200 ppm H2 gas at a temperature of 200 C, indicating quite a
possibility of much reduction in the operating temperature of the ZnO-based H2 gas sensors. The
ZnO wirelike film sensors showed a fast response to hydrogen gas in comparison with conventional
ZnO films. These results suggest that the ZnO wirelike films can be used as the gas sensing materials
for low-cost and high-performance gas sensors. 2009 American Vacuum Society.
DOI: 10.1116/1.3244563

I. INTRODUCTION structures reported, including thermal evaporation,8

Semiconducting metal oxide materials have been widely
used for gas sensors since the first observation of the gas
sensing effect in zinc oxide ZnO films by Seiyama et al.1 in
1962. These gas sensors are based on the phenomena that a
change in electrical conductivity of semiconducting metal
oxides is caused by the adsorption and desorption of gases.
In spite of their advantageous features such as small dimen-
sions, low cost, low power consumption, and good compat-
ibility with microelectronic processing, semiconducting-
metal-oxide-based gas sensors still have some limitations
such as high operating temperature, normally in the range of
300 500 C, poor gas selectivity, and low maximum
sensitivity.2,3
Zinc oxide, an n-type semiconductor with a wide direct
band gap of 3.37 eV at 300 K,4 has been extensively inves-
tigated for the detection of various gases such as NH3, NO2,
CO, H2, H2S, and ethanol vapors.2,3,518 Recently, ZnO-
based hydrogen gas sensors have attracted much attention
due to some important applications including combustion gas
detection in spacecraft and solid oxide fuel cells with proton-
exchange membranes.914 It is well recognized that the per-
formance of ZnO-based gas sensors is strongly dependent on
the dimension of the microstructures of the sensing material
ZnO.7 In this respect, ZnO nanostructures such as
nanowires,8 nanobelts,10,18 nanorods,1115,17 and
16
nanocomposites are very promising for improving the gas
sensing properties owing to their great surface-to-volume ra-
tio. There have been several synthesis methods of ZnO nano-
a
Electronic mail: hyojkim@cnu.ac.kr
sputtering,10,18 molecular beam epitaxy,1113
14,15 16
hydrothermal, and sol-gel method. However, it is hard
to obtain ZnO nanowires directly by sputtering even at high
substrate temperatures. Here, we attempt to synthesize ZnO
nanostructures by a simple method combined with sputtering
at low temperature, thermal oxidation of sputtered metallic
Zn nanostructured films in dry air, because a large scale of
uniform metallic Zn films is expected to be easily
deposited.1921
In this paper, we report on the hydrogen gas sensing char-
acteristics of ZnO wirelike thin films synthesized by thermal
oxidation of sputtered Zn wirelike films. The ZnO wirelike
film sensors exhibit a high sensitivity and reversible fast re-
sponse to H2 gas at an operating temperature as low as
200 C, illustrating that the ZnO wirelike films are promis-
ing materials for low-cost and high-performance gas sensors.
II. EXPERIMENT
To fabricate gas sensing elements based on ZnO wirelike
films, a pair of parallel Pt/ Ti electrodes was first deposited
on the SiO2 / Si 100 substrates by sputtering using a shadow
mask. Another shadow mask was then used to deposit ZnO
wirelike films onto the structure, resulting in a gas sensing
element comprising the ZnO-based active layer embedded
with Pt/ Ti parallel electrodes. The layout of a typical gas
sensing element can be found elsewhere.22
ZnO wirelike thin films were prepared two consecutive
steps. First, Zn metal films were grown on the SiO2 / Si sub-
strates with patterned Pt/ Ti electrodes from a pure Zn target
by a rf sputtering method in an Ar atmosphere of 5 mTorr.

1347 J. Vac. Sci. Technol. A 276, Nov/Dec 2009 0734-2101/2009/276/1347/5/$25.00 2009 American Vacuum Society 1347
1348 Hung et al.: Synthesis and hydrogen gas sensing properties of ZnO wirelike thin films 1348

FIG. 1. Typical XRD pattern of the ZnO wirelike film. The diffraction peaks
can be indexed according to the hexagonal wurtzite structure of ZnO.

The substrate temperature was kept at 100 C and the

substrate-to-target distance was set to be 12 cm. Second, the
as-deposited Zn films were then thermally oxidized in dry air
at a temperature of 400 C for 90 min using a rapid thermal
annealing system. The initial increasing rate of the annealing
temperature was kept at 20 C / min.
The crystalline structure of the ZnO wirelike films was
characterized by x-ray diffraction XRD using Cu K radia-
tion. Scanning electron microscopy SEM was used to ex-
amine the microstructures of the films. The H2 gas sensing
properties of the ZnO wirelike films were measured using a
homemade computer-controlled gas sensing characterization
system. For the current-voltage I-V measurements, the dc
voltage was fixed at 3 V and the change in current with time
was recorded. During the measurements, the H2 gas concen-
tration was varied in dry air with the total flow rate set at a FIG. 2. a Top-view and b cross-sectional SEM micrographs of the ZnO
constant value of 500 SCCM SCCM denotes cubic centime- wirelike film.
ter per minute at STP, and the operating temperature was
controlled using a small isolated hot plate integrated in the
measurement chamber.

grains. Given that the gas sensitivity of ZnO-based gas sen-

III. RESULTS AND DISCUSSION
Figure 1 shows a typical XRD pattern of the ZnO wirelike
films with a typical diameter of less than 100 nm and a typi-
cal length of several micrometers and their SEM micro-
graphs are presented in Figs. 2a and 2b. Apart from the Si
002 and 004 reflection lines from the substrate, the other
significant diffraction peaks can be indexed to the hexagonal
wurtzite structure of ZnO with lattice parameters of a
= 0.325 nm and c = 0.521 nm, in good agreement with the
standard XRD data for ZnO.23 No diffraction peaks corre-
sponding to the Zn metal phase are observed, indicating that
the as-deposited Zn metal films were completely oxidized
even at a low annealing temperature of 400 C. The small
additional peaks at 45, 49, and 62 are ascribed to the
Pt/ Ti electrodes. The average ZnO crystallite size was esti-
mated to be about 15 nm from the Scherrer formula24 using
three main diffraction peaks of ZnO 100, 002, and 101.
It is noted that the crystallite size estimated from the XRD
data is relatively small in comparison with the wire dimen-
sion observed from the SEM micrographs, implying that the
ZnO wire practically consists of a chain of many small
sors is mainly dependent on the dimension of the
microstructures,7 this kind of ZnO nanostructure having a
structure of large active surface area would result in high gas
sensitivity and low operating temperature.
The H2 gas sensing properties of the ZnO wirelike films
were measured for various H2 gas concentrations and oper-
ating temperatures. Linear I-V characteristics were observed,
indicating that Ohmic contacts were formed between the
wires and the electrodes. Figure 3a shows the resistance
response curves of a ZnO wirelike film sensor upon exposure
to H2 with a concentration of 200 1000 ppm in dry air at
operating temperatures of 200 and 300 C. The initial resis-
tance of the sensor is high and steady, whereas its resistance
decreases abruptly when it is exposed to H2 gas, exhibiting
n-type semiconducting behavior as expected. It is noted that
the magnitude of the resistance change increases with in-
creasing the H2 gas concentration for both operating tem-
peratures. Figure 3b shows the response curves of the sen-
sor for a H2 gas concentration of 200 ppm at various
operating temperatures of 150, 200, 250, and 300 C. It can
be seen that the response characteristics of the sensor depend

J. Vac. Sci. Technol. A, Vol. 27, No. 6, Nov/Dec 2009

1349 Hung et al.: Synthesis and hydrogen gas sensing properties of ZnO wirelike thin films
FIG. 3. Resistance response curves of the ZnO wirelike film sensor a for
various H2 gas concentrations in dry air at operating temperatures of 200 C
solid line and 300 C dashed line and b for a H2 concentration of
200 ppm at several operating temperatures.
on the operating temperature. Here, the lower initial resis-
tance at higher temperatures is ascribed to the semiconduct-
ing property of ZnO.
The gas sensing mechanism of most semiconducting
metal oxide sensors is based on a change in electrical con-
ductance or resistance due to the gas adsorption and desorp-
tion on the sensor surface. When a ZnO-based sensor is ex-
posed to air, oxygen from the ambient adsorbs on the
exposed surface of ZnO and forms an O, O2, or O2 ion by
capturing an electron from the ZnO conduction band.25 Thus,
considering that undoped ZnO is n-type, the ZnO wirelike
films are supposed to exhibit quite a high resistance in air.
When the sensor is exposed to a reducing gas such as H2 gas,
the H2 gas reacts with the adsorbed oxygen species, produc-
ing H2O molecules and releasing electrons back into the con-
duction band. This causes an increase in conductivity and, as
observed, the resistance of the ZnO wirelike films is
decreased.
The sensitivity Sg of semiconducting metal oxide gas sen-
sors for a reducing gas is usually defined as a ratio of the
change in conductance upon exposure to the target gas in dry
air G = Gg Ga over the conductance in dry air, Ga: Sg
= G / Ga = Ra Rg / Rg, where Ra and Rg are the electrical
resistance in dry air and upon exposure to the target gas in
dry air, respectively.26 Figure 4a shows the variation of the
sensitivity with operating temperature for the ZnO wirelike
film sensor at 200 ppm H2 exposure in dry air. It is clearly
seen that the sensitivity exhibits the maximum value of
283% at 200 C, which is higher than that of sputtered ZnO
films3 operated at around 350 C as well as that of ZnO
JVST A - Vacuum, Surfaces, and Films
1349
FIG. 4. Variation of the sensitivity Sg for the ZnO wirelike film a as a
function of operating temperature at 200 ppm H2 exposure in dry air and b
as a function of H2 gas concentration at three different operating tempera-
tures of 200, 250, and 300 C.
nanobelts10 at 300 C, but is quite lower than that of ZnO
nanorod arrays with a diameter less than 100 nm operated at
250 C.14 It should be noted that the optimum operating tem-
perature of 200 C for the ZnO wirelike films is relatively
low in comparison with conventional ZnO-based H2 gas sen-
sors operated at temperatures from 300 to 400 C. Figure
4b shows the variation of the sensitivity as a function of H2
gas concentration for the ZnO wirelike film sensor at various
operating temperatures. Obviously, the sensitivity of the ZnO
sensor exhibits a nearly linear increase with increasing the
H2 concentration up to 1000 ppm at all the temperatures of
200, 250, and 300 C. This suggests that the adsorbed oxy-
gen species at the surface of the ZnO wirelike film sensor is
mainly O.18
It is well known that the sensitivity of semiconducting
metal oxide gas sensors is attributed to the surface reaction
between adsorbed oxygen and target gas, which caused the
conductivity change G. Considering the fact that the domi-
nant surface reaction mechanism H2 + O H2O + e does
not change with temperature, the observed increase in the
sensitivity G / Gg with increasing the operating temperature
up to 200 C can be attributed to an increase in the H2 re-
sponse due to the enhancement of thermal activation27 and a
significant increase in G compared with the increase in Ga
with temperature. On the other hand, the decrease in the
sensitivity G / Ga with increasing temperature above
200 C is possibly due to the notable increase in Ga, as is
1350 Hung et al.: Synthesis and hydrogen gas sensing properties of ZnO wirelike thin films
FIG. 5. Variations of the response time with H2 gas concentration for the
ZnO wirelike film at various operating temperatures of 200, 250, and
300 C.
clearly seen in Fig. 3b. Also, at high temperatures, the H2
response or G could be decreased due to a possible degra-
dation of ZnO.
Among key parameters for a gas sensor is the response
time tr, which is usually defined as the time taken for the
sensor to attain 90% of the saturation resistance upon expo-
sure to the target gas.28 Figure 5 shows the variations of the
response time with the H2 gas concentration for the ZnO
wirelike film sensor at three operating temperatures of 200,
250, and 300 C. It is clearly seen that the response time
decreases with increasing the H2 gas concentration e.g., tr
= 1.5 min and 34 s for 200 and 1000 ppm H2 at 200 C,
respectively. Furthermore, it is obvious that the response
time of the sensor decreases with increasing the operating
temperature. For example, the response time decreases from
1.5 min to 46 s and from 34 to 12 s for 200 and 1000 ppm
H2, respectively, with increasing the temperature from
200 to 300 C. These observed behaviors of the change in
the response time with the H2 gas concentration and operat-
ing temperature seem to be correlated with an enhancement
of the interaction strength between the target gas hydrogen
and the sensing ZnO layer with increasing the H2 and/or the
operating temperature. Given the recent observations for the
laser-deposited ZnO films at an operating temperature of
180 C under H2 3% in air ambience by Brilis et al.9 tr
= 3.1 min and for the ZnO nanorod arrays upon exposure to
200 ppm H2 in dry air at an operating temperature of 250 C
by Wang et al.14 tr = 200 s, the ZnO wirelike films exhibit a
response faster than the ZnO nanorods. Compared with con-
ventional ZnO films, the observed faster response, lower op-
erating temperature, and higher sensitivity of the ZnO wire-
like films are most likely attributable to the relatively higher
degree of hydrogen adsorption due to the high surface-to-
volume ratio associated with the wirelike nanostructure.29 On
the other hand, compared with nanowire arrays, the ZnO
wirelike films exhibit lower sensitivity, but faster response
and recovery times. It follows from our results that the H2
gas sensitivity can be improved by increasing the surface-to-
volume ratio, but other sensing properties may depend on
J. Vac. Sci. Technol. A, Vol. 27, No. 6, Nov/Dec 2009
1350
other effects, e.g., crystallinity and surface properties, than
the surface-to-volume ratio, which needs to be studied
further.
IV. CONCLUSIONS
To summarize, the gas sensors using ZnO wirelike films
synthesized through thermal oxidation of sputtered Zn metal
films in dry air exhibited excellent H2 gas sensing properties.
In particular, the observed high sensitivity and fast response
to H2 gas at a comparatively low temperature of 200 C
would lead to a reduction in the optimal operating tempera-
ture of ZnO-based gas sensors. These features together with
the simple synthesis process demonstrate that ZnO wirelike
films are promising for the fabrication of low-cost and high-
performance H2 gas sensors operable at low temperatures.
ACKNOWLEDGMENTS
This work was supported by the National Research Labo-
ratory Program and BK21 program, Korea.
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JVST A - Vacuum, Surfaces, and Films