Journal of the Korean Physical Society, Vol. 57, No. 6, December 2010, pp.

1784∼1788

Synthesis and Gas Sensing Properties of ZnO Nanostructures

Nguyen Le Hung
Department of Materials Science and Engineering,
Chungnam National University, Daejeon 305-764 and
Department of Physics, Thai Nguyen University of Education, Thai Nguyen, Vietnam

Eunseong Ahn, Hooncheol Jung, Hyojin Kim∗ and Dojin Kim

Department of Materials Science and Engineering,
Chungnam National University, Daejeon 305-764

(Received 12 January 2010, in final form 22 May 2010)

We report on the gas sensing properties of ZnO nanostructures synthesized using a simple method
combined with sputtering and subsequent thermal oxidation of sputtered metallic films in dry air.
By controlling the sputtering condition, we achieved polycrystalline wurtzite ZnO films with a
flower-like structure consisting of nanoflakes with a thickness of ∼20 nm and a wire-like structure
having a width of 100 - 150 nm and a length of several microns for deposition temperatures of
room temperature and 150 ◦ C, respectively. From gas sensing measurements for NH3 , CO, and H2
in dry air, the gas sensors based on ZnO wire-like thin films showed quite better responses than
those based on ZnO flower-like thin films. The ZnO wire-like thin film gas sensors exhibited a high
sensitivity to NH3 with a maximum sensitivity as high as ∼300% for 20 ppm NH3 at an operating
temperature of 200 ◦ C and a detection limit of 2 ppm. In addition, the ZnO wire-like thin film gas
sensors also displayed good responses to CO and H2 exposures. These results illustrate that the
ZnO wire-like thin films are very promising for low-cost, high-performance gas sensors.

PACS numbers: 73.61.Ga, 81.05.Dz, 81.15.Cd

Keywords: Zinc oxide, Gas sensors, Nanostructures
DOI: 10.3938/jkps.57.1784

I. INTRODUCTION health at even ppm levels [9], developing highly sensi-

In the field of solid-state gas sensors, the past few
decades have found widespread applications for gas sen-
sors based on semiconducting metal oxides such as SnO2 ,
ZnO, TiO2 , WO3 , Bi2 O3 , etc. [1]. The operating prin-
ciple of these semiconducting metal oxide gas sensors is
based on the phenomenon that the electrical conductiv-
ity of a semiconducting metal oxide varies with the com-
position and the concentration of the gas atmosphere
surrounding it [2]. Among semiconducting metal oxides,
ZnO has been intensively studied for the detection of
various gases, such as H2 , CO, NH3 , NO2 , and ethanol
vapors [3–8]. To date, ZnO-based gas sensors with vari-
ous forms of ZnO, including bulk ZnO, conventional thin
films and nanostructured ZnO, have been demonstrated.
However, there are some limitations, such as low maxi-
mum sensitivity, poor gas selectivity, and high operating
temperature, in making commercial ZnO-based gas sen-
sors.
Because some toxic gases can affect human life and
∗ E-mail: hyojkim@cnu.ac.kr; Fax: +82-42-822-3206
-1784-
tive gas sensors has become very important. Recently,
many efforts have been made to improve the gas sens-
ing properties of ZnO-based gas sensors. On the one
hand, the use of dopants and/or catalytic elements was
considered as an effective way [3–5, 10]. On the other
hand, given that the performance of ZnO-based gas sen-
sors strongly depends on the fabric of the microstructures
of the sensing material ZnO [11], control of the grain size
and the surface morphology of the ZnO layer is expected
to be very promising for improving gas sensing prop-
erties. Thus, ZnO nanostructures, such as nanowires,
nanobelts, and nanorods, synthesized using sputtering,
molecular beam epitaxy, hydrothermal, thermal evapora-
tion and hydrolysis method have recently attracted much
attention [10,12–15]. We have attempted to control the
ZnO nanostructures by using a simple method combined
with sputtering and subsequent thermal oxidation of the
sputtered metallic films in dry air [16].
In the present paper, we report on investigations of
the gas sensing properties of ZnO flower-like and wire-
like nanostructures synthesized by thermal oxidation of
sputtered Zn metallic films in dry air. The gas sensors
based on ZnO wire-like thin films show quite better re-
Synthesis and Gas Sensing Properties of ZnO Nanostructures – Nguyen Le Hung et al.
sponses to NH3 , CO, and H2 at a relatively low operating
temperature than those based on ZnO flower-like thin
films, illustrating that these ZnO wire-like thin films are
promising materials for low-cost, high-performance gas
sensors.
II. EXPERIMENTS
ZnO flower-like and wire-like nanostructures were pre-
pared by using thermal oxidation of sputtered Zn metal-
lic films in dry air. The Zn metal films were first grown on
SiO2 /Si (100) substrates with patterned Pt/Ti electrodes
from a pure Zn target by a sputtering method at an rf
power density of 2.5 W/cm2 in an Ar atmosphere of 5
mTorr. The base pressure was below 1 × 10−6 Torr. Dif-
ferent substrate temperatures ranging from room tem-
perature to 150 ◦ C were chosen while the substrate-to-
target distance was set to be 12 cm. The as-deposited
metal films were then thermally oxidized in a quartz tube
furnace at atmospheric pressure in dry air at a temper-
ature of 400◦ for 90 min with the initial rate of increase
in the annealing temperature being kept at 20 ◦ C/min.
To investigate the gas sensing properties of these ZnO
nanostructures, we fabricated gas sensing elements based
on the ZnO nanostructures as the active layers embed-
ded with Pt/Ti parallel electrodes, as described in detail
elsewhere [16].
The crystalline structure of the ZnO nanostructures
was characterized by using X-ray diffraction (XRD) with
Cu Kα radiation. Scanning electron microscopy (SEM)
and transmission electron microscopy (TEM) were used
to examine the microstructures and the morphologies of
the nanostructures. The gas sensing properties of the
fabricated gas-sensing elements were characterized using
a homemade computer-controlled gas-sensing character-
ization system. The dc voltage was fixed at 3 V, and the
change in current (or resistance) with time was recorded.
The operating temperature was controlled using a small
isolated hot plate integrated in the measurement cham-
ber. The test gases were NH3 , CO and H2 with various
concentrations in dry air at a total flow rate of 500 sccm.
The gas sensitivity, S, for a reducing gas such as NH3 ,
CO, and H2 was determined by using the ratio of the
change in conductance upon exposure to the target gas
in dry air (∆G = Gg − Ga ) to the conductance in dry air
(Ga ): S = ∆G/Ga = (Ra − Rg )/Rg , where Ra and Rg
are the electrical resistances of the gas sensor in dry air
and upon exposure to the test gas in dry air, respectively.
III. RESULTS AND DISCUSSION
Figure 1 shows the XRD patterns of the synthesized
ZnO nanostructures for three different sputtering depo-
sition temperatures of room temperature (RT), 100 ◦ C
-1785-
Fig. 1. Typical XRD patterns of the synthesized ZnO
nanostructures for three different sputtering deposition tem-
peratures of room temperature (RT), 100 and 150 ◦ C.
and 150 ◦ C. For all three samples, apart from the Si
(002) and (004) diffraction lines from the substrate, the
other diffraction peaks can be indexed to the wurtzite
phase of ZnO (hexagonal, P 63 mc), in good agreement
with the standard XRD data file for ZnO (JCPDS-ICDD
No. 04-0831). No diffraction peaks corresponding to the
Zn metal phase could be observed, indicating that the as-
deposited Zn metal films were completely oxidized into
a ZnO phase even at annealing temperatures as low as
400 ◦ C. In addition, with increasing deposition temper-
ature from RT to 150 ◦ C, the diffraction peaks from the
ZnO phase become sharp and strong, indicating a higher
crystallinity for the ZnO nanostructure deposited at 150
◦
C.
Figures 2(a) and (b) show typical SEM images of the
synthesized ZnO nanostructures for two different sput-
tering deposition temperatures of RT and 150 ◦ C, re-
spectively. For the deposition temperature of RT, the
synthesized ZnO nanostructure was flower-like which was
built up by nanoflakes with a thickness of 15 - 25 nm,
as clearly seen in the typical high-resolution SEM image
shown in the inset of Fig. 2(a). In contrast, for the depo-
sition temperature of 150 ◦ C, we synthesized a wire-like
ZnO nanostructure grown in a random orientaion with a
wire diameter of less than 150 nm and a length of sev-
eral µm. Actually, as clearly demonstrated by the typi-
cal TEM image shown in the inset of Fig. 2(b), the ZnO
wire consists of a chain of many small crystallites. From
the Scherrer formula [17], the average ZnO crystallites
is estimated to be about 20 nm by using the XRD data
corresponding to the deposition temperature of 150 ◦ C
in Fig. 1. These results obviously illustrate that various
kinds of ZnO nanostructures can be readily formed by
using the sputtering deposition temperature of the Zn
metal films.
The gas sensing properties of the fabricated gas sen-
sors based on ZnO flower-like and wire-like thin films
-1786- Journal of the Korean Physical Society, Vol. 57, No. 6, December 2010
Fig. 2. Typical top-view SEM images of the synthesized
ZnO nanostructures for two different sputtering deposition
temperatures of (a) room temperature and (b) 150 ◦ C. The
insets in (a) and (b) show the corresponding high-resolution
SEM and TEM images, respectively.
Fig. 3. Sensitivity as a function of the operating tempera-
ture for the ZnO flower-like and wire-like thin-film gas sensors
upon exposure to 20-ppm NH3 in dry air. The inset shows
typical resistance response curves of the gas sensors upon ex-
posure to 20-ppm NH3 in dry air at an operating temperature
of 200 ◦ C.
were measured at various operating temperatures and
gas concentrations. Figure 3 shows the sensitivity ver-
sus operating temperature for the ZnO flower-like and
wire-like thin-film gas sensors upon exposure to 20-ppm
NH3 in dry air. The sensitivity of the ZnO wire-like thin
film gas sensor reaches a maxium value of about 300%
at an operating temperature of 200 ◦ C, which is more
than twice the maximum sensitivity (about 120%) of the
ZnO flower-like thin-film gas sensor achieved at 200 ◦ C.
It is also several times higher than the sensitivity of con-
ventional ZnO films operated at elevated temperatures
from 300 to 400 ◦ C [4, 8]. In addition, the optimal op-
erating temperature of 200 ◦ C in the detection of NH3
is lower than those for other ZnO nanostructures [4, 8,
13]. These results imply that ZnO wire-like thin-film
gas sensors have high sensitivity to NH3 at a lower tem-
perature. On the other hand, the inset of Fig. 3 displays
typical resistance response curves for the ZnO flower-like
and wire-like thin-film gas sensors to 20-ppm NH3 in dry
air at the optimal operating temperature of 200 ◦ C. The
resistance for both the gas sensors is clearly seen to be
reduced in the presence of NH3 . It is worth noting that
the ZnO wire-like thin film gas sensor exhibits a quite
short response time and recovery time compared to the
ZnO flower-like thin film gas sensor.
The gas sensing mechanism of the ZnO-based gas sen-
sors for a reducing gas such as NH3 can be explained as
follows: When a ZnO-based gas sensor is exposed to air,
considering that ZnO is intrinsically an n-type material,
oxygen from the ambient will adsorb on the exposed sur-
face of ZnO and form an O− − 2−
2 , O or O ion by capturing
electrons from the ZnO conduction band [18,19]. Takata
et al. [19] revealed that the dominant adsorbed oxygen
species in ZnO are O− −
2 , O , and O
2−
for temperatures
below 100 C, between 100 and 300 ◦ C, and above 300
◦
◦
C, respectively. When the sensor is exposed to a reduc-
ing gas, the gas will react with surface-adsorbed oxygen
species, thus causing a change in the resistance of the
sensor. At 200 ◦ C, the dominant surface interaction be-
tween the reducing gas NH3 and the adsorbed oxygen
species can be expressed as follow:
2NH3 + 3O− → 3H2 O + N2 + 3e− .
That is, by releasing electrons back into the ZnO con-
duction band and increasing the carrier concentration in
the ZnO active layer, the sensor’s resistance is decreased
upon exposure to a reducing gas, as observed in the inset
of Fig. 3.
Figure 4(a) shows the resistance response curves of the
ZnO wire-like thin-film gas sensor to various NH3 concen-
trations in dry air at the optimal operating temperature
of 200 ◦ C. The response characteristics of the sensor is
clearly seen to sensibly depend on the NH3 concentra-
tion, exhibiting an increase in sensitivity with increasing
NH3 concentration. It should be noted that the detec-
tion limit of the ZnO wire-like thin film gas sensor to
NH3 in dry air may be below 2 ppm. Figure 4(b) shows
the sensitivity as a function of NH3 concentration for
the ZnO wire-like thin-film gas sensor operated at 200
◦
C (dots). This sensor is seen to have a wide detection
range for NH3 from 2 to 100 ppm. Actually, the ob-
served increase in the sensitivity of the semiconducting
oxide gas sensor with increasing target gas concentration
can be empirically represented as S = Ag (Pg )β , where
Synthesis and Gas Sensing Properties of ZnO Nanostructures – Nguyen Le Hung et al.
Fig. 4. (a) Resistance response curves of the ZnO wire-like
thin-film gas sensor to various NH3 concentrations in dry air
at the optimal operating temperature of 200 ◦ C. (b) Sensitiv-
ity (S) versus NH3 concentration (Pg ) in dry air of the ZnO
wire-like thin-film gas sensor operated at 200 ◦ C. The solid
line is the fit curve of the empirical model, S ∝ (Pg )β .
Pg is the partial pressure of the target gas, which is pro-
portional to the gas concentration, Ag is the prefactor
and β is an exponent [20]. In our case, the value of β is
found to be about 0.94 ± 0.02, as determined from the
fitting curve shown as the solid line in Fig. 4(b). This
value closely approaches the ideal value of 1 for the pri-
mary adsorbed oxygen species O− [21], and is consistent
with the observation by Takata et al. [19] for ZnO.
The response of the ZnO wire-like thin-film gas sen-
sor to other reducing gases such as CO and H2 was also
examined. Figure 5 shows the relative response curves
(normalized to a gas concentration of 1 ppm) of the ZnO
wire-like thin film gas sensor upon exposure to NH3 ,
CO, and H2 measured at 200 ◦ C. The ZnO gas sensor
is clearly seen to be sensitive to both CO and H2 . How-
ever, the relative sensitivities to CO and H2 are lower
than that of NH3 , which presumedly correlates with the
difference in the surface reaction strength between the
target gas and the sensing ZnO layer.
Compared with conventional ZnO thin films, the ob-
served enhancement in the gas sensing properties of the
ZnO wire-like thin-film gas sensor is most likely at-
-1787-
Fig. 5. Relative response curves of the ZnO wire-like thin-
film gas sensor upon exposure to NH3 , CO, and H2 measured
at 200 ◦ C.
tributable to the relatively higher degree of surface reac-
tion due to the high specific surface area associated with
the wire-like nanostructure. On the other hand, com-
parison with ZnO flower-like and other nanostructures
leads us to conclude that the gas-sensing properties also
depend on other effects, including crystallinity and sur-
face properties, and this needs to be studied further.
IV. CONCLUSIONS
In conclusion, ZnO flower-like and wire-like nanostruc-
tured thin films have been synthesized through thermal
oxidation of sputtered Zn metallic films in dry air. The
deposition temperature during the sputtering process
was found to be a key parameter to control the mor-
phology of the ZnO nanostructured thin films. Com-
pared with the ZnO flower-like thin-film gas sensor, the
gas sensor fabricated from a ZnO wire-like thin film was
found to exhibit excellent gas sensing properties for NH3 ,
CO, and H2 . In particular, the ZnO wire-like thin-film
gas sensor shows a highly sensitive response to NH3 at
relatively low temperatures and even at low NH3 concen-
tations. These results, along with the simple synthesis
route, demonstrate the promising feasibility of fabricat-
ing low-cost, high-performance ZnO-based gas sensors.
ACKNOWLEDGMENTS
This work was supported by the National Research
Laboratory Program and the BK21 program, Korea.
The authors also acknowledge the financial support by
Basic Science Research Program through the National
Research Foundation of Korea (NRF) funded by the Min-
istry of Education, Science and Technology (R01-2008-
000-20014-0 and 2010-0004327).
-1788- Journal of the Korean Physical Society, Vol. 57, No. 6, December 2010

REFERENCES sors, edited by C. A. Grimes, E. C. Dickey and M.

V. Pishko (American Scientific Publishers, Stevenson
Ranch, 2006), p. 413.
[1] Solid State Gas Sensing, edited by E. Comini, G. Faglia
[12] A. Z. Sadek, S. Choopun, W. Wlodarski, S. J. Ippolito
and G. G. Sberveglieri (Springer, New York, 2009).
and K. Kalantar-Zadeh, IEEE Sens. J. 7, 919 (2007).
[2] T. Seiyama, A. Kato, K. Fujishi and M. Nagatani, Anal.
[13] J. X. Wang, X. W. Sun, Y. Yang, H. Huang, Y. C. Lee,
Chem. 34, 1502 (1962).
O. K. Tan and L. Vayssieres, Nanotechnology 17, 4995
[3] J. Müller and S. Weibenrieder, Fresenius J. Anal. Chem.
(2006).
349, 380 (1994).
[14] Q. Wan, Q. H. Li, Y. J. Chen, T. H. Wang, X. L. He, J.
[4] G. Sberveglieri, S. Groppelli, P. Nelli, A. Tintinelli and
P. Li and C. L. Lin, Appl. Phys. Lett. 84, 3654 (2004).
G. Giunta, Sens. Actuators, B 24, 588 (1995).
[15] J. Xie, P. Li, Y. Wang and Y. Wei, J. Phys. Chem. Solids
[5] D. F. Paraguay, M. Miki-Yoshida, J. Morales, J. Solis
70, 112 (2009).
and L. W. Estrada, Thin Solid Films 373, 137 (2000).
[16] N. L. Hung, E. Ahn, S. Park, H. Jung, H. Kim, S-K.
[6] J. F. Chang, H. H. Kuo, I. C. Leu and M. H. Hon, Sens.
Hong, D. Kim and C. Hwang, J. Vac. Sci. Technol., A
Actuators, B 84, 258 (2002).
27, 1347 (2009).
[7] Y. Min, H. L. Tuller, S. Palzer, J. Wöllenstein and H.
[17] B. D. Cullity, Elements of X-ray Diffraction (Addison-
Böttner, Sens. Actuators, B 93, 435 (2003).
Wesley, Reading, 1978), p. 102.
[8] G. S. Devi, V. B. Subrahmanyam, S. C. Gadkari and S.
[18] M. Che and A. J. Tench, Adv. Catal. 31, 77 (1982).
K. Gupta, Anal. Chim. Acta 568, 41 (2006).
[19] M. Takata, D. Tsubone and H. Yanagida, J. Am. Ceram.
[9] NIOSH Pocket Guide to Chemical Hazards, 3rd ed. (Na-
Soc. 59, 4 (1976).
tional Institute for Occupational Safety and Health,
[20] R. W. J. Scott, S. M. Yang, G. Chabanis, N. Coombs,
Cincinnati, 2007).
D. E. Williams and G. A. Ozin, Adv. Mater. 13, 1468
[10] L. C. Tien, P. W. Sadik, D. P. Norton, L. F. Voss, S. J.
(2001).
Pearton, H. T. Wang, B. S. Kang, F. Ren, J. Jun and J.
[21] S. C. Naisbitt, K. F. E. Pratt, D. E. Williams and I. P.
Lin, Appl. Phys. Lett. 87, 222106 (2005).
Parkin, Sens. Actuators, B 114, 969 (2006).
[11] S. Ahlers, G. Müller and Th. Doll, Encyclopedia of Sen-