2C3.

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A HIGH PERFORMANCE ETHANOL GAS SENSOR BASED 0 N C d 0-Fe, O3 1(3EM1 C 0 N D U C T I N G M A T E R I A L S

Xingqin Liu, Zhengliang X u and Yusheng Shen D e p a r t m e n t o f Materials Science and Engineering University of Science and T e c h n o l o g y of China Hefei. Anhui 230026 C h i n a

Abstract

on the composition Fe,O, materials.

optimized C d O -

A novel ethanol s e n s o r based on CdO-Fe,O, system o x i d e semiconductor has been developed. T h e performance of the sensor, including sensitivity, selectivity, stability as well a s the response and recovery times, have been examined and s t u d i e d . T h e results demonstrate that a11 characteristics o f the s e n s o r s are excellent. This indicates it a nice ethanol sensor and p r o m i s i n g for practical and potential applications.
Keywords: ethanol sensor , CdG-Fe,O,, oxide semiconductor Introduction
There has been a great effort to develop gas sensors for e t h a n o l because po f its practical significance. CdSnO,[l], ZnSn0,[2] and Fe20,[3] based semiconductors a s a k i n d o f good ethanol gas sensing materials have been extensive 1y studied. H o w e v e r , their sensitivity and selectivity t o ethanol need t o be further improved. Recently we have found that C d O a d d i t i o n into Fe,O, can dramatically e n h a n c e i t s gas sensing characteristics. A study o n the influence of C d / F e ratio a n d preparation conditions o n the conductivity and gas sensing property o f t h e materials was addressed. In this paper w e present the excellent characteristics o f a high performance ethanol g a s s e n s o r based

Experimental

A m i x e d salt solution with specific C d / F e m o l e ration w a s prepared b > dissolving analytical pure C d S 0 , . 8 / 3 H 2 0 and F e ( N 0 , ) , . 9 H , O into water. T h e powder of CdO-Fe,O: system w a s obtained by chemical c o p r e c i p it at i o n w i t h aq u e o u s amrn o n i a t o control p H value in 9.7 - 10.5, and then d r y i n g , grinding and calcining at different temperatures. G a s sensing elements of external heating t y p e were fabricated by a thick film technique in w h i c h a paste m a d e of a proper CdO-Fe,O, p o w d e r and an organic binder was painted o n a small ceramic t u b e and fired at 6 0 0 "C for 3 hr., and t h e n aged at 3 0 0 "C for a week. The conductance of the elements was measured at the temperature ranging from r o o m temperature to 5 5 0 " C . And the gas sensing properties of the elements w a s studied in a way that the element w a s placed in a static container with the testing gas o f specific concentration. T h e gas sensitivity(S) is defined as the ratio o f the element resistance(Ra) in air t o that in testing gas(Rg).
Results and D i s c u s s i o n s
F i g u r e 1 s h o w s the plots of the Conductance vs. tenipcratur.: of a scnsor

0-7803-3829-4/97/$10.00997 IEEE 0 1

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2C3.11P i n diffesent a m b i e n t . The c o n d u c t a n c e i n argon m o n o t o n o u s l y increases with temperature and is about two o r d e r o f
magnitude h i g h e r t h a n that i n both air and oxygen. The much lower conductance v a l u e s i n the a m b i e n t that the oxygen a d s o r b o n the s u r f a c e of the gas sensing material and capture electrons from t h e bulk e l e m e n t to become charged o x y g e n s p e c i e s . The same c o n s i d e r a t i o n c a n also well

'O01

Air

'1

X
X

0
P
2

&

3
3

100

200

300

400

500

T ( T )

been f o u n d i n S n O , based gas sensing s e m i c o n d u c t o r s [ 4 ] . When t h e reducing gas is inlet into the ambient it reacts with the s u r f a c e charged oxygen species to release electrons into bulk that results i n a s u d d e n decrease o f the element resistance. T h i s is t h e principle o f the gas s e n s i n g property f o r the oxide semiconductors o f surface control t y p e . And i t is e x p e c t e d that t h e s a m e gas sensing m e c h a n i s m is valid for C d O F e 2 0 , s y s t e m materials a s they exhibit the s a m e e l e c t r i c behavior like S n 0 2 . The very l o w c o n d u c t a n c e o f the sensor in oxygen containing ambient. compared w i t h that without o x y g e n , would predict a good sensitivity to seducing g a s e s . Figure 2 p r e s e n t s the s e n s i t i v i t i e s of t h e sensor to a number of g a s e s i n the temperature r a n g e from 2 0 0 "C to 430 O . I t can b e seen that t h e senr.rr C exhibits not o n l y a very h i g h sensitivity hut also very good selectivity to ethanol, a b o u t 1 0 t i m e s h i g h e r than that for other tested gases i n c l u d i n g petrol ,

Figure I . The s e n s o r conductance vs. ( temperature scanning temperature rate: 30 " C / m i n )

explain t h e f a c t that the sensor conductance in pure oxygen i s lower than that i n air because o f different oxygen c o n c e n t r a t i o n . The e x i s t e n c e of the m a x i m u m conductance values appeased at 3 0 0 "C and 320 "C , respectively i n air a n d in pure o x y g e n is resulted f r o m t h e c o m b i n a t i o n o f two me c h an i s m s : t h e i n t r i n s i c c o n d u c t atic e of the s e m i c o n d u c t o r which increases with t e m p e r a t u r e m o n o t o n o u s l y j u s t like in a r g o n and t h e a d s o r p t i o n of oxygen o n t h e materials surface mentioned a b o v e , which leads t o a drop in sensor c o n d u c t a n c e depending on the temperature. T h i s is well k n o w n as surface c o n t r o l l e d behavior w h i c h has

IOOppm ethanol
A

1000ppm petrol 100pppm petrol 1000ppm LPG 1000ppm CO

b
\

30

+
+

250

300

350

400

450

Operating temperature (y:)

Figure 2. Se n s i t iv i t y vs. Te m p e rat u r e of a sensor t o d i f f e r e n t g a s e s

L P G and C O . T h e sensitivity to 100 ppm ethanol is f i v e t i m e s higher t h a n that to 1000 ppm p e t r o l . Figure 3 is t h e plots of

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2C3.11P
sensitiviry values o r a sensor to ethanol and petroi a s a function of their concentrations. Obviously, there is a n essentially linear behavior in the concentration range from less than looppin up to a t least 1000 p p m . ethanol b u t also the good stability of its sensitivity t o a l l tested gases. This may suggest i t s potential applications f o r detecting ethanol as we11 a s other chemical species in t h e gaseous mixture In order to further check t h e stabilit) and durabljity c!f the sensor, the elcnients wei'c u n d e r g o n e the scrisitivitr measu rem e n t aft er a1t erna t i v e 1 y ag i n g at 300 "C in air for s o m e d a y s a n d laying a s i d e in the atmosphere at room temperature f o r some d a y s . A t y p i c a l result is presented in Table 1 J t can be seen that during over 70 days the sensitivities t o both e t h a n o l and hydrogen h a v e been 110 chaiip,c. Thiy indicares t h a t the sensor malerial i. quite stabie and i t s g a s sensing property is a l m o s t iiot influenced b y othcr chemicCii s p e c i e s in a t m o s p h e r e . I t s110:tld be noted tll;it t h e qenso:s show a v e r y rapid response io the testing g a s . A s typically s h o w n i n Figure 5 , the response t i m e , which is defined a s the time f o r reacbing 90% of the full response change o f the sensor when testing gas inlets, is [vithin 2-3 seconds, and the recovery is done almost instantly

70

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601
501
40
A

C,H,OH
petrol
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7'

, "

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L A -

.
200

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of

400

600

800

Gas Concentration ( ppm )

r igure 3. Concentration depdndence

the gas sensitivity f o r sensor r r 2 300

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6oi 50-1 /
404

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A

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petrol LPG

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, ,

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t t

10

20

30

40

50

tt

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60

Ageing time ( days )

Figure 4 . G a s sensitivity vs. time f o r a sensor operating at 300 C'

i I

A s indicated by Figure 4, the sensitivities o f a n as-prepared sensor to the tested g a s e s have gradually become better and better in first ten days and t h e n k e e p c o n s t a n t . This f i g u r e d o e s not on1.r tell us t h e excellent selcctivity to

Figure 5. Response una' recoverj' Characleristics of a sensor operaring at diffi*r e n I !e m p e r (1; tu r e

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2C3.11 P
Table I . The stability of the sensor performance
time (days) S(R,/R,)
(300 C)

ageing (in air, 300 C ) laying aside (room temp. air)

4
11

27
2

8 15 51 6.5

C,H,OH( 1000ppm)
H, (1000ppm)

48
6

50
6.2

52
6.4

53
6.2

50
6.0

51
6.3

Conclusion
We have developed a new ethanol gas sensor based o n CdO-Fe,O, oxide semiconductor materials. The sensor is of surface controlling t y p e and exhibits very good performance and characteristics: (1) high sensitivity with a linear behavior to ethanol in [he concentration range f r o m less t h a n 1 OOppm to o v e r 1OOOppm ( 2 ) excellent selectivity t o ethanol agairlst other CQmmoi! g;lses which may coexist with ethanol, s u c h as petrol, H,, C O , LPG and other hydrogencarbon chemicals. ( 3 ) good stability and durability of the performance at operation temperature and i n atmosphere, and (4) a1 m o st instant response and re c o v 2 r y be h av i or . T h e excellent performance surely makes this novel sensor an useful ethanol sensor and promising for s o m e potential applications in practice.

Acknowledgment
T h e financial s u p p o r t f r o m National Natural Science Foundation of China is sincerely a c k n o w l e d g e d .

References
[ l ] T. Zhang, Y. S h e n and R. Zhang, Pestructure-type f3 - C d S n O , used as an ethanol sensing material, Materials Letters 23( 1995)69 Y.Shen and T. Z h a n g , Preparation, s t r u c t ur 2 and gas - s e ri s i 11 prop er t i e s g of ultramicro Z n S n O , p o w d e r , Sensors and Actuators B , 1 2 (1 9 9 3 ) 5 X.Liu, S . Tao, Y . S h e n and G. Meng, Preparation a n d Character iza t i o n of Nanocrystalline a -Fe,O, by a Sol-gel Process, Sensors and Actuators, in print, 1997 [4] M . Nitta, S. Otani and H a r a d o m e , Temp er atur e D e p e n d e c e o f Resistivities o f S n 0 , - B a s e d Gas Sensors E x p o s e d to CO,H,,and C,H, Gases J . Electronic Materials, 9(4)( 1980)727

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