Direct current conductivity and oxygen gas-sensing properties of ironantimonytellurite glasses

S. Chakraborty, H. Satou, and H. Sakata Citation: J. Appl. Phys. 82, 5520 (1997); doi: 10.1063/1.366542 View online: http://dx.doi.org/10.1063/1.366542 View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v82/i11 Published by the AIP Publishing LLC.

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Direct current conductivity and oxygen gas-sensing properties of ironantimonytellurite glasses

S. Chakraborty,a) H. Satou, and H. Sakatab)
Department of Applied Chemistry, School of Engineering, Tokai University, 1117, Kitakaname, Hiratsuka, Kanagawa 259-12, Japan

Received 20 November 1996; accepted for publication 24 August 1997 Iron tellurite glasses in the system Fe2O3 SbTeO2 have been prepared by the melt-quenching technique. The glass forming region for the above system has been determined. A comparative study of the direct current electrical conductivity, , of the 15Fe2O3 5Sb80TeO2 mol% glass together with 15Fe2O3 5Sb2O3 80TeO2 and the binary 15Fe2O3 85TeO2 glass has been made in the temperature range 463598 K. The 15Fe2O3 5Sb80TeO2 glass was found to be most conductive 1.39 10 5 S cm1 at 503 K in this series. The semiconducting behavior of these glasses could be explained by the small polaron hopping model. The oxygen gas-sensing property of the 15Fe2O3 5Sb80TeO2 glass was investigated. The O2 gas sensitivity at 598 K was found to be 8.1. The variation in conductivity on alternate switching of gas atmospheres between oxygen and argon was found to be reproducible. An attempt has been made to clarify the mechanism of conductivity response considering the phenomenon of surface adsorption followed by bulk diffusion. From the investigation of the gas-sensing behavior, the present glass was found to be a potential candidate for an oxygen gas sensor. 1997 American Institute of Physics. S0021-89799701323-6

I. INTRODUCTION

Recently there has been a considerable interest in the study of semiconductive glasses with tellurium oxide as the glass former. Tellurium oxide is a nonconventional glass former as under normal conditions it cannot go into the glassy state without a modier. Binary and ternary tellurite glasses were mainly studied for optical applications14 for their good infrared transmittivity. Only a little work has been done on the electrical applications of these glasses.59 The conductivity of the binary Fe2O3 TeO2 glasses are known to be several orders of magnitude higher than that of the silicate, borate, and phosphate glasses with the same amount of iron.10 Such a remarkable increase in the conductivity of tellurite glass is speculated to be due to the unshared pair of electrons of the TeO4 group, which do not take part in the bonding. We were stimulated to study ternary irontellurite glasses11,12 mainly to seek glasses of higher conductivity. From the application point of view, we expected the highly conductive tellurite glasses to be potential candidates for oxygen gas sensors. O2 gas sensors have wide applications in industrial, medical, environmental, and sanitation elds. Such sensors studied earlier were mainly zirconia type13,14 and oxide semiconductor type.15,16 It is noteworthy that hardly any work has been done to exploit the gassensing behavior of semiconductive oxide glasses.17,18 Hence a parallel study of the dependence of conductivity changes on gas atmosphere was undertaken in our endeavor to seek an O2 gas-sensing material.
II. EXPERIMENT

Reagent grade 99.99% purity Fe2O3, TeO2, Sb2O3, and Sb were used as raw materials. The required components in
a

On leave from the Indian Association for the Cultivation of Science, Jadavpur, Calcutta-700 032, India. b Electronic mail: skt@keyaki.cc.u-tokai.ac.jp 5520 J. Appl. Phys. 82 (11), 1 December 1997

prescribed compositions were well mixed in appropriate proportions in an argon atmosphere for Sb containing glasses. A batch of 5 g was melted in an electrical furnace, at a temperature of 1073 K for 30 min, in an argon atmosphere. The melt was then quickly quenched between two copper blocks kept at room temperature. The glass formation region was determined by x-ray diffraction analysis using Philips PW1820 diffractometer. The four-point probe method with a distance of 2 mm between the probes was used to measure the direct current dc conductivity in the temperature range 463598 K. The electrodes were fabricated in a co-planer geometry with silver paste. A constant dc current of 0.1 A was applied during measurements. The values of the dc conductivity of a sample in different runs agreed within 1% and for samples of the same composition in different batches the agreement was about 2.5% at 583 K. Within the temperature range of measurement, no polarization due to ionic currents was observed, which indicates that the conduction in the present system of glasses was electronic. The thermoelectric power of the glass samples was measured in air keeping a temperature difference of 510 K between the surfaces. The negative sign of the Seebeck coefcient conrms the glasses to be n -type semiconducting. The detailed results on the measurement of Seebeck coefcient will be published elsewhere. It was noted that the oxidation state of the components of the bulk glass does not change on atmospheric exposure. For the study of the O2 gas sensing property, the 15Fe2O3 5Sb80TeO2 mol% glass was dry crushed in air in an agate mortar. A pellet of the powdered sample 1 mm in thickness and 14 mm in diameter was prepared in air at 277 MPa. It was then sintered in air for 3 h at 603 K, which is below the glass transition temperature ( T g ) of 632 K, as determined from differential thermal analysis. A constant current of 0.1 A was applied during measurements, where a four-point probe technique was used. Each atmospheric gas
1997 American Institute of Physics

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FIG. 1. The glass formation region of the Fe2O3 SbTeO2 system. glass; crystallized.

FIG. 3. Temperature dependence of dc conductivity in air for 15Fe2O3 5Sb80TeO2mol%, 15Fe2O3 5Sb2O3 80TeO2mol%, and 15Fe2O3 85TeO2mol% glasses.

owed independently into the furnace chamber at the ow rate of 1 l /min. The particle size of the pellet was determined from the scanning electron micrograph Model: Elionix Co. ESA-2000 of the pellet surface.
III. RESULTS AND DISCUSSION A. Glass formation region

T 503 K we nd that the 15Fe2O3 5Sb80TeO2 glass was the most conductive in the series studied with 1.39 10 5 S cm1. The corresponding values of conductivities for other glasses are listed in Table I for comparison. The semiconductive behavior in these Fe ion containing glasses11,12 is usually due to hopping of small polarons between Fe ions in different valence states. A general formula for conductivity in these glasses as given by Mott21 is

Figure 1 shows the glass formation region of the Fe2O3 SbTeO2 system. The composition range for the glass formation was found to be 0 Fe2O3 20 mol%, 0 Sb 25 mol% and 70 TeO2 100 mol%. This glass formation region was found to be small like that of other tellurite glasses8,19,20 but was wider than that of the Fe2O3 Sb2O3 TeO2 system studied earlier.11 Figure 2 shows the x-ray diffractrogram of the 15Fe2O3 5Sb80TeO2 mol% glass showing the amorphous character.
B. Electrical conduction

phe 2 C 1 C R 2 N exp 2 R exp W / kT ,

In general the electrical conductivity of the Fe2O3 SbTeO2 glasses increased monotonically with the increase in Fe2O3 content in the glass. Figure 3 shows the plots of log(T) versus T 1 in air atmosphere, in the temperature range of 463598 K for the 15Fe2O3 5Sb80TeO2 glass together with that of 15Fe2O3 5Sb2O3 80TeO2 and the binary 15Fe2O3 85TeO2 glasses for a comparative study. For Fe2O3 5Sb80TeO2 ( x 10 20) glasses we found the relationship log 523 KFe2O3. From the conductivity values of the different glass samples at a xed temperature say,

where ph is the phonon frequency, is the rate of wave function decay constant, C is the ratio of concentrations of the ions in the lower valence state to the total concentrations of the transition metal ions, W is the activation energy for conduction, N is the number of transition metal ion Fe sites per unit volume, R is the average spacing between transition metal ions, e is the electronic charge, k the Boltzmann constant, and ( kT ) 1 , where T is the absolute temperature. Equation 1 can be compared to the Arrhenius equation given by

0 exp W / kT / T .
In Eq. 1, W is given by W W H 1/2W D and WWD
for T D /4 ,
22

for T D /2 ,

TABLE I. Chemical composition, conductivity , and activation energy for conduction ( W ) of the glasses. The value of W in air was obtained by the tting of the data in Fig. 3. Glass composition nominal mol % 15Fe2O3 85 TeO2 15Fe2O3 5Sb2O3 80TeO2 15Fe2O3 5Sb80TeO2 FIG. 2. The x-ray diffraction 15Fe2O3 5Sb80TeO2mol% glass. pattern CuK of the
a b

C Fe2/ W (eV) (Fe3Fe2a 503KS cm1 498598 K 0.10b 0.443 0.466 5.2110 6 7.03210 6 1.397 10 5 0.630 0.621 0.588

Obtained by chemical analysis Refs. 11 and 12. From Ref. 10. Chakraborty, Satou, and Sakata 5521

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with W H as the hopping energy and W D as the disorder energy arising from the energy difference of the neighboring ions between the hopping sites,22 and D is the Debye temperature. In the temperature range of measurements 463598 K, the relation between log(T) and T 1 is found to be linear Fig. 3 and conforms to Eq. 1. Since no change in the slope of the Arrhenius plots is observed from Fig. 3, the activation energy is considered to be single-valued. Hence we can conclude that hopping occurs uniquely through the Fe ions along the FeOFe chain, contrary to the case of the iron containing bismuth vanadate glasses.23 Compared to the binary Fe2O3 TeO2 glass, for glasses containing Sb2O3 or Sb, the C value Fe2/Fe2 Fe3 )] increased remarkably as seen in Table I because of the redox reaction between Sb2O3 or Sb. Similar observation was made by Naitoh et al.24 for V2O5 Sb2O3 P2O5 glasses and Mori et al.6 for V2O5 Sb2O3 TeO2 glasses. For the Fe2O3 SbTeO2 glasses, the redox reaction during melting occurred as follows: 3Fe2O32Sb6FeOSb2O3. 3

FIG. 4. Scanning electron micrograph of the surface of the pellet of 15Fe2O3 5Sb80TeO2mol% glass. scale: 5 m.

The theoretically estimated C value ( C cal) using the above equation was in good agreement with the experimentally obtained values from chemical analysis11 for different compositions of the glasses in the Fe2O3 SbTeO2 series Table I; e.g., we obtained C cal 0.5 for 15Fe2O3 5Sb80TeO2 glass C 0.443, Table I. This obviously means that Sb acted as a reducing agent in the glass. The C value for the 15Fe2O3 5Sb80TeO2 was higher than that of the 15Fe2O3 5Sb2O3 80TeO2 and the binary 15Fe2O3 85TeO2 glasses Table I. This explains the higher conductivity in the Sb-containing glass considering the preexponential term C (1 C ) in Eq. 1. As a consequence of the Sb-induced redox reaction, the C value increased, increasing the conductivity in the glasses. The values of W as obtained from the slopes of the experimental curves in Fig. 3, by the method of least squares tting are listed in Table I. Again, comparing Eqs. 1 and 2 we nd

The ratio of the pellet density after heat treatment and atmospheric exposure to the bulk density was found to be 0.47, which is smaller than the case for 62.3V2O5 4.3Sb2O3 33.3TeO2 glass18 where it was 0.81 which corresponds to 19% of porosity, indicating a relatively higher porosity 53% of the present material. The mean particle size in the pelleted glass sample as determined from Fig. 4 was between 1 and 2 m. In the following sections we shall discuss the effect of different gas atmospheres on the conductivity and study the dynamic changes in conductivity of the sample on alternate switching of Ar and O2 gases every hour at a constant temperature.
1. Conductivity response to oxygen and argon gases

0 ph NC 1 C e 2 R 2 / k exp 2 R .

For the 15Fe2O3 5Sb80TeO2 glass, N 7.422 1021 cm3 as estimated from the density value (6.482 g cm3), R (1/N ) 1/3 was estimated to be 5.1265 10 8 cm, assuming 1 0.2 and ph11013 Hz, log 0 was then calculated to be 3.96 which is close to the value of 4.15, as obtained by the tting of the experimental data in Fig. 3 with Eq. 1. Hence the semiconducting behavior in these transition metal oxide glasses appear to be due to the small polaronic hopping between transition metal ions of different valence states.

Figure 5 shows the inverse temperature ( T 1 ) dependence of dc conductivity of the pellet sample in O2, Ar, and air atmospheres in the temperature range 571614 K. The experimental relationship between log(T) and T 1 under air, oxygen, and argon atmospheres was tted to Eq. 2 using the least squares tting method with r 2 values as 0.9989, 0.9985, and 0.9987, respectively, where r is the correlation coefcient. A satisfactory t conrms that electrical conduction in argon and oxygen gas atmospheres was also due to the hopping of small polarons, similar to that in air for

C. Oxygen gas-sensing properties

We expected that the highly conductive tellurite glasses should exhibit O2 gas-sensing behavior since a vanadium tellurite glass showed O2 gas sensitivity, although it was relatively low.18 Therefore the 15Fe2O3 5Sb80TeO2 glass was selected for this purpose.
5522 J. Appl. Phys., Vol. 82, No. 11, 1 December 1997

FIG. 5. Temperature dependence of conductivity for 15Fe2O3 5Sb80TeO2mol% pelleted glass sample in different gas atmospheres: Ar gas, air, and O2 gas. Chakraborty, Satou, and Sakata

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gas is adsorbed at the glass surface because of its relatively high porosity 53%, as mentioned earlier. When the glass is exposed to O2 atmosphere, O2 physisorption occurs in the outmost surface of the glass as O2O2adsorbed. 5

Assuming the adsorption site in the glass to be Fe2 ions on account of the high C value 0.466, from Table I, the physisorped O2 reacts rapidly with Fe2 at the surface, capturing electron from Fe2, i.e.,
3 O2adsorpedFe2O 2 Fe .

FIG. 6. a Changes in conductivity of 15Fe2O3 5Sb80TeO2mol% glass with time at 598 K on alternate switching to Ar and O2 gases. The solid lines are calculated using Eqs. 10 and 13. b Changes in conductivity of 15Fe2O3 5Sb80TeO2mol% glass between 55 and 68 min at T 598 K, showing the sudden change in conductivity from 60 to 61 min.

the as-quenched glass, as mentioned in Sec. III B. The study of the effect of different gas atmospheres on revealed that decreases in an oxygen atmosphere while it increases in the presence of argon gas. The activation energy for conduction, estimated from the slope of the curves in Fig. 5, by the least squares tting technique, were 0.648 eV in Ar, 0.683 eV in O2, and 0.674 eV in air, respectively, for T 571 614 K. Thus we nd the activation energy to be lower in Ar but higher in O2 than in air, similar to the case of the ternary vanadium tellurite glass.18 It should be noted that the conductivity in air of the pellet sample Fig. 5 was one order of magnitude less than that of the as-quenched glass Fig. 3. The probable explanation could be due to increased surface resistance due to the increased surface area of the pellet containing many neck parts between grains which was produced on pelletizing of the glass.
2. Dynamic changes in gas-induced conductivity

Figure 6a represents the changes in dc conductivity of the sample glass with time ( t ) on alternate switching to atmospheric O2 and Ar gases at every hour at 598 K. The overall response of conductivity to the changes in gas atmosphere was that increased in argon atmosphere and then decreased when switched to oxygen atmosphere. This essentially means that Fe2 ions in the glass were oxidized by O2 gas to Fe3 ions resulting in an increase in Fe3 ions with time and hence a decrease in . On changing the atmosphere from Ar to O2, there was a sudden decrease of conductivity by 80% in about 1 min inset Fig. 6b followed by a gradual decrease with time. In our attempt to explain the glassgas interaction mechanism for the present system, we speculated that the conductivity response can be described by two successive processes of surface adsorption of gas quick process followed by its diffusion into the bulk slow process. We know the conductivity change due to gas adsorption occurs very rapidly, from less than 1 min25,26 to several min27 after introducing the gas. So the rapid change in conductivity is expected to be associated with surface reactions which modulate the carrier concentration.28 The O2
J. Appl. Phys., Vol. 82, No. 11, 1 December 1997

This negative charge adsorption chemisorption causes a rapid decrease in carrier concentration at the outermost surface which leads to the formation of a subsequent depletion layer near the semiconductor surface. The decrease in Fe2 decreases the rate of the exchange reaction, Fe2Fe3 e , at the surface. This effect may be striking at the grain boundary of the particles, which produces an insulating neck for the carrier transport. The effect, therefore, strongly depends on porosity of material, since in our previous study on O2 gas-sensing behavior of vanadiumtellurite glass,18 using a glass sample with a small porosity of 19%, we did not observe the rst step of conductivity change due to adsorption Fig. 6a. So the rapid change in conductivity in the exchange of Ar for O2 due to adsorption is caused by the high porosity 53% of the sample. Then say for 61 t 120 min in Fig. 6a the chemisorbed oxygen gradually diffuses into the glass bulk, because of a relatively high temperature, accompanied by a gradual decrease in conductivity. Inversely, on exposing the O2-diffused glass to Ar atmosphere, the Ar is rst adsorbed physically at the surface and then diffuses into the glass bulk. The gradual increase in conductivity from 121 t 180 min during the ow of argon gas was due to a desorption-controlled process where the dissolved O2 gas diffuses out gradually from the glass bulk and desorbs from it. Thus, the reverse reaction of Eqs. 5 and 6 takes place bringing forth an increase in the carrier density and hence in conductivity. Such gradual changes in conductivity could be well interpreted by the oxygen diffusion and desorption model17,18 as described below. The glass sample with a layer of diffused oxygen can be thought of as a rectangular sheet with an electrode spacing as L , electrode width as W , sample thickness d ( d W ), and the oxygen diffusion layer of thickness X ( X d ) on either side of the sheet. Considering the conductivity of the bulk glass to be b and that of the diffused oxygen layer as s , the average conductivity for the present method of measurement is expressed as29

b X / d ,

where b s . Now on introducing O2 gas into the system, the O2-diffused layer increased with the elapsed time. Then the thickness X of the layer, measured from the glass surface to the interior is given by30 dX / dt CDV 0 / X k / X ,
Chakraborty, Satou, and Sakata

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TABLE II. Parameters and calculated using Eqs. 10 and 13.

Temperature K 598 Time h Gas atmosphere 1.43 10 0t1 Ar

7

(S cm 3.38 10 1t2 O2
1

min
1/2

) 1.63 10 8 3t4 O2

4.32 10 8 2t3 Ar

The O2 gas sensitivity ( S ), which was dened as the ratio of the initial resistivity to that in a sample gas as estimated from Fig. 6a considering the ratio of the rst plateau to the rst valley was found to be S 8.1 at 598 K. This is about one order of magnitude higher than of the 62.3V2O5 4.3Sb2O3 33.3TeO2 glass,18 where the adsorption effect was not found.
IV. CONCLUSION

where C is a constant, D is the diffusion coefcient of oxygen, and V 0 is the volume of an O2 atom, k CDV 0 . Integrating Eq. 8 we obtain the parabolic increase of X with t as X 2 2 kt . From Eqs. 7 and 9 we get 9 10

t b t 1/2,

where (2 k ) 1/2/ d . When the introduced gas was switched from O2 to Ar, after the O2 diffusion layer reached a thickness, say, X X 0 at time t t 0 , then the dissolved oxygen in the glass diffused out again from the surface.17 The relationship between the thickness of the oxygen diffused out layer X , as measured from X 0 to the surface at the time t , is given by d X / dt k / X , 11 where k C D V 0 , with C as a constant and D is the diffusion coefcient of the case where the oxygen molecules occluded in the glass are rediffused by the inow of the argon gas. Thus, D and D are likely to differ. Integrating Eq. 11 we get
X X 0 2 2 k t t 0 .

A new ternary irontellurite glass system, viz. Fe2O3 SbTeO2 was obtained. From a comparative study of the dc conductivities, the 15Fe2O3 5Sb80TeO2mol% was found to be more conductive with 1.39 10 5 S cm1 at 503 K than the 15Fe2O3 5Sb2O3 80TeO2 and 15Fe2O3 85TeO2 glasses. The mechanism of conduction in these glasses was attributed to be by the process of hopping of small polarons. The oxygen gas sensitivity ( S ) of the 15Fe2O3 5Sb80TeO2 glass on alternate switching to O2 and Ar atmospheres was S 8.1 at 598 K, which was the highest among the reported results on semiconductive glasses, thereby suggesting its practicality as an O2 gas sensor. The interesting feature was that such semiconductive materials with polaronic type conduction mechanisms responded to the changes in gas atmospheres.
ACKNOWLEDGMENTS

One of the authors S.C. would like to thank the Matsumae International Foundation and the Tokai University for nancial support. The authors would also like to thank Dr. H. Mori, Kyoto University, for valuable discussions.
M. Imaoka and K. Satake, Seisan Kenkyu 9, 505 1957 in Japanese. A. K. Yakhkind, J. Am. Ceram. Soc. 49, 670 1966. 3 M. S. Redman and J. H. Chen, J. Am. Ceram. Soc. 50, 523 1967. 4 R. O. Heckroot and M. A. Res, Phys. Chem. Glasses 17, 217 1976. 5 H. Hirashima, M. Ide, and T. Yoshida, J. Non-Cryst. Solids 86, 327 1986. 6 H. Mori, T. Kitami, and H. Sakata, J. Non-Cryst. Solids 168, 157 1994. 7 H. Mori, J. Igarashi, and H. Sakata, Glastech. Ber. 68, 327 1995. 8 H. Mori, T. Kitami, and H. Sakata, J. Ceram. Soc. Jpn. 101, 347 1993. 9 H. Mori, J. Igarashi, and H. Sakata, J. Ceram. Soc. Jpn. 101, 1351 1993. 10 L. Murawski, J. Mater. Sci. 17, 2155 1982. 11 H. H. Qiu, H. Mori, H. Sakata, and T. Hirayama, J. Ceram. Soc. Jpn. 103, 32 1995. 12 H. H. Qiu, H. Sakata, and T. Hirayama, J. Chinese Ceram. Soc. 24, 58 1996. 13 T. Usui, Y. Kurumiya, K. Nuri, and M. Nakazawa, Sens. Actuators 16, 345 1989. 14 A. M. Azad, A. Akbar, S. G. Mhaisalkar, L. D. Birkefeld, and K. S. Goto, J. Electrochem. Soc. 139, 3690 1992. 15 A. Takami, Ceram. Bull. 67, 1956 1988. 16 L. Ketron, Ceram. Bull. 68, 860 1989. 17 H. Sakata, M. Amano, Y. Kawashima, and T. Okamoto, J. Ceram. Soc. Jpn. 102, 317 1994. 18 H. Mori and H. Sakata, Mater. Chem. Phys. 45, 211 1996. 19 H. Hirashima and T. Kawaguchi, Seramikkusu-Ronbunshi 97, 1144 1989. 20 H. Hirashima and H. Tanaka, Seramikkusu-Ronbunshi 97, 1150 1990. 21 N. F. Mott, J. Non-Cryst. Solids 1, 1 1968. 22 I. G. Austin and N. F. Mott, Adv. Phys. 18, 41 1969. 23 R. Singh and K. Sethupati, J. Phys. D 22, 709 1989. 24 T. Naitoh, T. Namekawa, and K. Maeda, J. Ceram. Soc. Jpn. 100, 685 1992.
1 2

12 13 14 15

Combining Eqs. 7 and 12 we have

t 0 t t 0 1/2 for t t 0 ,
where

t 0 b X 0 / d ,
and

2 k 1/2/ d .

Figure 6a shows the experimental plot of log and t , together with the theoretical curves using Eqs. 10 and 13. The values of and for different runs are listed in Table II. In Table II, and decreased with time t , the reason being that the diffusion coefcients D and D decreased with time. The fact that in Fig. 6a, the second plateau 120180 min is lower than the rst plateau 060 min, i.e., at t 3 h was lower than that at t 1 h, was because the conductivity value was not recovered because the dissolved O2 did not completely diffuse out from the glass surface. Therefore an introduction of Ar gas for more than 1 h was necessary to restore the value. Any possibility of bulk oxidation 60 120 min seems unlikely because it is prevented by the occluded Ar gas in the sample. The conductivity response followed a similar pattern to Fig. 6 when tested at another temperature of 583 K.
5524 J. Appl. Phys., Vol. 82, No. 11, 1 December 1997

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25

T. Seiyama, A. Kato, K. Fujiishi, and M. Nagatani, Anal. Chem. 34, 1502 1962. 26 S. Matsushima, D. Ikeda, K. Kobayashi, and G. Odaka, Chem. Lett. 2, 323 1992. 27 M. Akiyama, J. Tamaki, N. Miura, and N. Yamazoe, Chem. Lett., 9, 1611 1991.

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J. Vetrone, Y. W. Chung, R. Cavicchi, and S. Semancik, J. Appl. Phys. 73, 8371 1993. 29 A. Kobayashi, in Semiconductors, 11th ed. Iwanami Shoten, Tokyo, 1972, p. 189 in Japanese. 30 N. F. Mott, in Conduction in Non-Crystalline Materials Oxford University Press, Oxford, 1987, Ch. 9, 9.3.

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