NmoSbru& Makrials. Vol. 8, No. 7, pp.

815-823, 1997
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GAS SENSING PROPERTIES OF NANO-ZnO PREPARED

BY ARC PLASMA METHOD

L.F.Dong, Z.L. Cui and Z.K. Zhang

Research Center of Nanostructured Materials,

Qingdao Institute of Chemical Technology, 266042 Qingdao, China

(Accepted October 2,1997)

Abstract - Nanometer ZnO. &O-Fe were prepared by Hz+Ar arc plasma method.
Compared with coarse-grained ZnO, nano-ZnO evidentlypossesses grain-size effect and the
operating temperaturesshifttowarda lowertemperature(200 “c-300 “c). The sensitivityof ZnO
increases with&creasing grain size. Nano-ZnOexhibitshigher sensitivitiesto LPG and C2H2
than toH2 and CO. Compared withnano-ZnOand ZnO-Ag,nano-ZnO-Fe-Agexhibitsexcellent
selectivityto Hz withhigh sensitivityat < 200°C and the response time is less than 15s. Thus,
nano-ZnO-Fe-Agholdspromiseasa low-powerselectiveHz gas sensor. 01998 ActaMetallurgica
Inc.

1. INTRODUCTION

Although ZnO is one of the earliest metal oxides used as gas sensing materials, ZnO gas
sensors seldolmcan be found in commercial applicationmainly because of its lower sensitivity and
higher operating temperature. In general, its operating temperature is 400”C-450°C (1). Even
when doped with noble metals, such as Pt, Pd, its sensitivity is still lower than Sn@ series of gas
sensors. For example, Pt may improve sensitivities to ethane, propane, isohexane, etc., but the
maximum of the sensitivities to CH4is no more than 8 and those to H2and CO are less than 3. Pd
doping ZnO gas sensor has certain sensitivity and selectivity,but its sensitivities to CO and H2are
7.5 and 9.5 mspectively, which are much lower than SnOzseries of gas sensors. The concentration
of the detection gases mentioned above is 5000 ppm (2,3).

2. EXPERIMENTAL

2.1 Preparation of Gas Sensing Materials

Nano-ZnO was prepated in two steps. First, nano-Zn particles were prepared by the H2+Ar
arc plasma method. The preparationprocessing and parametershave been described in refs. 4 and
5. Second, nano-Zn particles were oxidized in air at 300°C for 0.5h and were further oxidized at
600°C for 1h.

815
816 LF DONG,ZL GUIANDZK ZHANG

Nano-ZnO-Fe was also prepared in two steps. Under otherwise identical conditions, a
mixture of bulk Zn:Fe = 3: 1 in weight ratio was placed on the fixed copper anode. The bulk Fe
together with Zn was melted and evaporated by the high temperature of the plasma. Zn-Fe
nanoparticles were formed by the nucleation and growth process through collision of the
metal-metal atoms and the metal-gas atoms (or molecules).
ZnO-Fe-Ag andZnO- Ag were obtained by impregnations of aAgN03 solution into ZnO-Fe,
ZnO particles. The impregnated particles were dried at 100°C for 0.5 h and calcinated in air at
300°C for 0.5 h and 600°C for 1 h.

2.2 Characterization

X-ray diffraction (XRD) analysis was used to study the phase structure of gas sensors
(D-max-rAdiffractometer). The mean particlediameter was estimated from transmission electron
microscope (JEM2OOOEXelectron microscope) and Scherrer’s equation of x-ray diffraction.

2.3 Fabrication of Gas Sensors and Gas SensitivityMeasurements

To fabricate sensor elements, the nano-metal oxides were cold-pressed at 450 MPa into a disc
(8 mm in diameter and 0.5 mm in thickness), inside which a pair of NiCr wire electrodes (0.14 mm
in diameter) were embedded 2 mm apart. The pressed disc was then heat treated in air at 600°C
for 1 h.
Hydrogen (Hz), carbon monoxide (CO), ethane (CzH2) and liquefied petroleum gas (LPG)
were used as the gases to be measured. The change in resistance of the gas sensor was measured
when a reducing gas, such as CO, H2 or C2H2 was introduced by a gas syringe into the test chamber
(see Figure 1).

II

Figure 1. Schematic diagram of gas element test system: l-Test chamber, 2-Thermocouple,
3-Gas element, 4-Heater , and E--Resistance recorder.
GASSENSING
PRCERTIES
OFNANO-ZNO
PREPARED
BYARCPUSMAMETHW 817

Figure 2. TEM microgmph of nano-ZnO.

ar -1

lM.0 rsoa am.0 2x10 3m.u

Tetnperutrro “C

Figure 3. G-T curve of nano-ZnO (60 nm).

818 LF DONG,ZL GUIANOZK ZHANG

18

18

14 t
1
ZnO 42
mC2H2

p
g

(3
12
10

6
i
t
I
I
-40
*LFG

8 . ..
4 /.’ ” \-. . ..
-_-.&-- I
x0 230 300
T-0 oc
Figure 4. G-T curve of nano-ZnO (200 nm).

According to the test requirements, an accurate quantity of detection gas was introduced.
When the G-T (Sensitivity-Temperature)curve of the gas sensor was studied, the concentration of
the detective gases in the test chamber was 5000 ppm. When the G-C (Sensitivity-Concentration)
curve of the gas sensor was studied, the temperaturewas constant and the concentration decreased
gradually.
The sensitivity (G) is expressed by the ratio of the resistance measured in air (Ra) to that
measured in the presence of reducing gases( Rg), G = Ra/Rg.

3.1 RESULTS AND DISCUSSION

3.1 Size Eflect

Figure 2 shows the microstructure of nano-ZnO particles. The average particle sixes are
about 60 nm (left), and 200 nm (right) respectively. Compared with coarse-grained ZnO gas
sensor,nano-ZnO gas sensor whoseaverageparticle sizewas 60 nm exhibitsremarkably enhanced
gas sensing properties. Figure 3 shows that the sensitivitiesto LX and C2H2are almost the same,
about 16. In general, the operating temperature of a conventional ZnO gas sensor is 400-45O”C,
while Figure 3 shows that the nano-ZnO gas sensor has maximum sensitivities to LFG and C2H2
at around 250°C and 22O”C,respectively. It is clear that the maximum sensitivities shift towards
lower temperatures.
To study the reasons that nano-ZnO gas sensor can improve gas sensing properties, a ZnO
gas sensor whose average particle size was 200 nm was fabricated. Figure 4 shows that with
increasing particle size, the sensitivities decrease. The maximum sensitivity to all the four gases
is no more than 7. With particle size decreasing from 200 nm to 60 nm, the sensitivity to LPG
rapidly increased from 1.3 to 15.6.
 GAS SENSING PROPERTIESOF Nmo-ZNO PREPAREDBYARC PLASMA
METHOO 819

Figure 5. R-T curve of doped ZnO gas elements.

-c

t0 A h

.d!Ld
0

.
.. .
. jl,i.;l
t
.

n ?B m m II II II

Figure 6. ED of ZnO, ZnO-Fe, ZnO-Ag, and ZnO-Fe-Ag.

820 LF DONG,ZL GUIAND ZK ZMNG

TABLE 1
Particle Size of Ag, ZnO, ZnFqO4 Calculated using Scherrer Formula (nm)

(x10! rad) (L)

ZXlO ZIlO 18.136 0.32 45.1

zno-Fe ZllO 18.125 0.32 45.1
We204 17.616 0.34 42.3
ZnO-Ag ZIIO 18.144 0.32 45.1
Ag 19.077 0.32 45.3
ZuO-Fe-Ag ZnO 18.144 0.32 45.1
ZnFezOs 17.641 0.32 44.96
Ag 19.082 0.34 42.67

18: 2#Fe

0
42
16 : +C2H2
14 A0

12 dFG
Q 10 r

8:
6: P- -0

4;

2:

0
30.0 imn 1sM

soa 1m.a lsO.O anO mo smo -50 im 15~ a~ 250 300

Tunpuatln T Tm#ratW°C

Figure 7. G-T curve of doped ZnO gas elements.

 GAS SENSING PROPERTIESOF NANO-ZNO
PREPAREOBY ARC PLASMA
METHOD 821

The results show that the gas sensing properties of ZnO evidently possess grain-size effect.
More and more people think that the tendency to develop gas sensing materials further is to make
the particle size reach nanoscale. For example, o-Fe203 is generally gas-insensitive because of
its high chemical stability. However, o-Fe203 with the fine crystallites and low crystallinity
exhibits remarkable gas sensitivity (6,7,8).
The gas sensing properties of nano-ZnO differs significantly from those of ZnO due
probably to an increase in the surface dangling bonds and/or a change in the electronic structure
due to quantum size effects with decreasing particle size. On the other hand, hydrogen, which must
be used during preparation, caused the structure change of the nano-metal and the defects was
observed by TEM (9).

3.2 AdditiveE;fect

3.2.1 Effect of the additiveson the electrical properties of nano-ZnO

The resistance of a gas element fabricated from nano-ZnO was over 150 KQ at 200°C in air.
This resistance value is so high that a precise measurement of the resistance change caused by
reducing gases is difficult without sufficient amplification. Therefore, several metal cations like
Pd2+, Fe3+ and Ag+ were used to dope ZnO by an impregnation method in order to increase its
N-type semiconductivity. The resistance of the elements prepared from the doped ZnO were
measured in aiu as a function of the temperature and the results are shown in Figure 5.
The resi;stance of nano-ZnO-Ag element was 16KfJ at 200°C in air, nearly one tenth of that
of ZnO element. Pd only reduces the resistance of ZnO element in higher temperatures. The
resistance of ZnO-Fe element is similar to that of ZnO element.

3.2.2 Ejvectof the additiveson the gas sensingproperties of nano-ZnO

Figure 6 shows the x-ray diffraction patterns of ZnO, ZnO-Fe, ZnO-Ag, and ZnO-Fe-Ag.
The results show that Ag in ZnO-Ag and ZnO-Fe-Ag exists as the form of Ag metal, Fe in ZnO-Fe
and ZnO-Fe-Ag exists in the form of ZnFezOs compound. At the same time, as shown in Figure
6, the addition of ZnFe204 or Ag does not promote the broadening of the x-ray diffraction patterns
of ZnO. Therefore these additives are not inducing finer crystallinity to ZnO. The grain sixes of
Ag, ZnFe204 and ZnO calculated using the Scherrer formula are shown in Table 1(1=0.15405 1
nm and FWHM were used).
Compared with nano-ZnO, ZnO-Fe-Ag and ZnO-Ag have apparent improvement in
selectivity and sensitivity (see Figure 7). The sensitivities of ZnO-Ag to QH2 and H2 arc 42 and
26, respectively. The sensitivity of ZnO-Fe-Ag to H2 is 57.
The operating temperatures of ZnO-Ag to C2H2 and H2 are 12O’C. The operating
temperature of ZnOFe-Ag to H2 is 17O’C. Theoperating temperatureofAg doping ZnO or ZnO-Fe
has been decreased by 230-33O’C compared to that of the coarse-grained ZnO.
Figure 8’shows furthermore that ZnO-Fe- Ag possesses excellent selectivity to Hz with a high
sensitivity against CO, C2H2 and LPG, which may be developed to act as Hz gas sensor. When G-C
curve was studied, the selected temperature is the best temperature at which the sensitivity to
detective gas i.smaximum. The selected temperature to Cfl2 is 1lO”C, those to HZ, LPG and CO
are 172OC.
822 LF DONG,ZL GUIAND
ZK ZHANG

an
a0
b-l
*ii2
42H2
ZrGFeAg/-
i
y 16

16

I4

12

10

4
7

Figure 8. G-C curve of ZnO-Fe-Ag. Figure 9. Response time curve of ZnO-Fe-Ag.

Compared with nano ZnO-Ag, ZnO-Fe-Ag possesses excellent selectivity to H2 as a result

of the ZnFe204 dopant. Although the gas sensing properties of ZnO-Fe are not better than ZnO,
the interaction between ZnO, Ag and ZnFe204 contributes to the improvements observed above.

3.3 The Response and Resumption Time

Figure9showsthatthesensitivityofZnO-Fe-Agreached63%(1-l/e)ofthefinalsteady-state
signal after 10 s for 5000 ppm LFG at 400K (140°C). This response at such a low temperature can
be considered to be sufficiently rapid. The resumption time is less than 30 s.

4. CONCLUSIONS

The gas sensing properties of ZnO is affected by grain-size. In particular, the sensitivity
increases rapidly with decreasing grain size into the nanophase regime. NanoZnO prepared by
H2+Ar arc plasma method possesses excellent gas sensing properties.
Ag and Fe additives not only decrease the resistance of ZnO in air, but also greatly improve
its gas sensing properties. ZnO-Fe-Ag element possesses high sensitivity and excellent selectivity
to Hz against Cfl2, CO, and LPG. At the same time, the response time is less than 15 s at 15O”C,
indicating that ZnO-Fe-Ag can be used as a low power, selective H2 gas sensor.
The preparation device, a hydrogen arc plasma system, can produce 100 g per hour. Since
the mass of sensing elements is less than 100 mg, thousands of nano-ZnO gas elements can be
fabricated with the nanoparticles prepared in one hour. That method, therefore, is highly efficient
for the production of gas sensing material.
 OF NAW-ZNOPREPAREDBYARC PLASMAMETHOD
GAS SENSINGPROPERTIES 823

ACKNOWLEDGMENT

The authors would like to thank Chuncheng Hao, Zhaoguo Meng, Liyan Yu, and other
colleagues for their help with the experiments. This work was supported by the State Planning
Commission of China and Natural Science Foundation of Shandong Province.

REFERENCES

1. Seiyama, ‘T.,et al. Material Science, 1972; 8.63.

2. Katsura,hd.,et al., Proceedings of thelnternationalMeeting on Chemical Sensor, Fukuoka,Japan,
Kondansha Lta, Tokyo, Elsevier, Amsterdam, 1983.
3. Matsuzawa T., et al., Proceedings of the International Meeting on Chemical Sensor; Fukuoka,
Japan, Kondansha Lta, Tokyo, Elsevier, Amsterdam, 1983
4. Cui, Z.L. and Zhang, Z.K., Nanostructured Materials, 1996,7(3), 355.
5. Cui, Z.L., Dong, L.F. and Zhang, Z.K., Nanostructured Materials, 1995,5(7), 829.
6. Nakatani,Y., Sakai,M. andMatsuoka,M., Japanese JournalofAppliedPhysics. 1983,22(6), 912.
7. Dong, L.R, Cui, Z.L. and Zhang, Z.K., Journal of Functional Materials, 1995,26 (Suppl). 416.
8. Cui, Z.L. and Dong, L.F., Journal of Functional Materials, 1995,26(4), 321.
9. Zhang, Z:K., Cui, Z.L., Chen, K.Z., et al., Journal of Materials Science and Technology, 19!96,12,
75.

Published without the benefit of authors’ final corrections as they were not available at press time.