Electrochimica Acta 52 (2007) 67716777

Diffusivity of anion vacancies in WO3 passive lms

Gerardo V azquez, Ignacio Gonz alez ,1
Universidad Aut onoma Metropolitana-Iztapalapa, Depto. de Qu mica, Area de Electroqu mica, Apdo. 55-534, C.P. 09340, M exico D.F., Mexico Received 1 February 2007; received in revised form 25 April 2007; accepted 25 April 2007 Available online 6 May 2007

Abstract The WO3 lms were grown in 0.1 M HClO4 aqueous solution, at different formation potentials (Ef ) in the range of 2.07.0 V versus sce, on W electrode. The anion diffusion coefcient (DO ) of WO3 lms was calculated from EIS spectra, following the surface charge approach (at high-eld limit approximation), the Point Defect Model and the MottShottky analysis. Among the parameters necessary to evaluate DO , the half-jump distance (a) is very relevant, given that a small variation in a has a great impact in the calculation of DO . In this work, it is proposed is taken from lattice the half-jump distance (a) should be evaluated from spectroscopic data (available in the literature). The value of a (1.9 A) constants of a-WO3 (amorphous-WO3 ), with different values of N (coordination number), and the lattice constants of m-WO3 (monoclinic-WO3 ). The calculated value of DO was 3 1017 cm2 /s. 2007 Elsevier Ltd. All rights reserved.
Keywords: Diffusivity; Passive lms; EIS; W oxides; MottSchottky

1. Introduction The WO3 has an increasing importance on new technologies such as exible smart windows [1] due to its electrochromic properties [25], WO3 can be used as electrochemical functional material, in thermal control applications and active layer, as well as gas sensing applications [6], where WO3 shows an excellent sensitivity to H2 S and other gases, such as: NOx and CO [7]; it can be used in the photoelectrochemical degradation of dyes, such as naphthol blue black diazo [8], among other applications. The mechanism to describe the growth of passive lms can be explained by the Point Defect Model (PDM) [911], the PDM considers that the oxide lm contains a lot of point defects (e.g. anionic and cationic vacancies and metal interstitials). The transport of point defects within the lm could be due to the existence of a high electric eld (106 107 V/cm) and the movement of point defects within the lm is associated with the growth of the lm. This idea was essentially rst proposed by Verwey [12], and later by other authors, such as: Mott and Cabrera [13,14]. The transport of point defects within the lm
1

can be quantitatively described by their diffusivity. An effort to calculate the anion vacancies diffusivity (DO ) in oxide passive lms, has been performed by the surface charge approach developed by Bojinov [15]. Among the parameters necessary to evaluate DO in the surface charge approach, the half-jump distance (a) is very relevant (i.e. 2a equals the lattice constant of the unit cell). The values obtained by Bojinov for a, in the WO3 lms, in different acid media, are in the range of 1.82.5 A [15]. Since a very small variation in the value of a has a great in impact in the calculation of DO (e.g. differences of 0.5 A the value of a changes DO in 1 order of magnitude), then it is very important to have an accurate value of a, and use a as known parameter in the calculation of DO . 1.1. Overview Diffusivity of the point defects in WO3 , has been calculated by Sikora et al. [16]. The approach of this paper started with the NernstPlanck equation and by means of the Point Defect Model (PDM) computed the anion vacancy diffusivity (DO ), a value of 1014 1015 cm2 /s was obtained. However, the surface charge approach developed by Bojinov [15], suggests that the equation used by Sikora et al., in calculating DO , is associated to the low-eld limit approximation of a more general equation

Corresponding author. Tel.: +52 58044671; fax: +52 58044666. E-mail address: igm@xanum.uam.mx (I. Gonz alez). ISE member.

0013-4686/$ see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2007.04.102

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given by Fromhold [17]. The equation of Fromhold at the higheld limit approximation seems to be a better option in order to calculate DO , due to the assumption of the existence of high eld strength within the oxide passive lm. 1.2. Anion vacancies in the WO3 The exact nature of the WO3 lms with regard to their being crystalline or amorphous is not easy to ascertain. Apparently, very thin lms on valve-metals tend to be amorphous or microcrystalline [18]. Thermodynamically, the tungsten cations in the oxide lm are found in a very high oxidation state (+6); then the formation energy of cation vacancies is expected to be much higher than that for the oxygen vacancies, this is true only in the bulk of the oxide. However, the reactions of generation of defects at the metal/lm and lm/solution interfaces are much more energetically favorable, and the activation energies for the electrochemical reactions for the generation of positive defects at the metal/lm interface and negative defects at the lm/solution interface might not be so different. The dominant point defects in the passive lms can be elucidated directly by determining the oxygen/metal ratio through the lms [19] and indirectly by MottSchottky plots (MS analysis). The use of these plots has been object of controversy, due to the frequently observed non-linearity for the metal/oxide lm/electrolyte junctions; this behavior has been attributed according to Tomkiewicz [20] to: non-homogeneus doping levels, deep doping levels, among others. However, none of these appears to provide a viable explanation of the entire form of the MS plots, found for many metal oxides in presence of different electrolytic media. Another issue in MS plots is the change of the measured capacitance with frequency. The change with the frequency for thin anodic WO3 lms, was associated with the amorphous nature of the oxide [18]. Nevertheless, Pajkossy [21] attributes the CO (Lss ) = CO (0) exp Lss a th zFaE0 RT a sh DO

be the dominant defect (majority carriers), which gives to the WO3 the n-type semiconductor character, then the density of donors (ND ) could be measured by the MS analysis and correlated with the concentration of donors near the interface metal/ lm [16]. 1.3. The density of donors (ND ) according to PDM The detailed explanation of PDM can be reviewed in several papers [911], this paper is concerned only with the ND as a function of Ef (Eq. (1)) given by Sikora et al. [16]. Sikora et al. started from the NernstPlank equation, concluding that the density of donors (ND ) is given by the following relationship (Eq. (1)). CO (Lss ) = ND = w1 exp bEf + w2 (1)

where CO (Lss ) is the concentration of oxygen vacancies at the metal/lm interface, at which they are generated (therefore, their concentration at this interface is the highest), ND the density of donors in the passive lm, w1 and b the unknown constants and Ef is the lm formation potential. w2 is given by [16]: w2 = JO RT zFE0 DO (2)

where Jo is the steady-state ux of donors, F the Faraday constant, E0 the mean electric eld strength, R the gas constant and T is temperature (K). 1.4. The density of donors (ND ) by the surface charge approach Bojinov [15] started with Eq. (3), which is a more general equation for CO (Lss ), given rst by Fromhold [17]. zFaE0 RT + JO 1 exp Lss a th zFaE0 RT (3)

dispersion of the capacitance, to the roughness of the surface (not necessarily of an amorphous material). The semiconductor properties are more clearly manifested in crystalline materials than in amorphous ones, because in amorphous materials the recombination could be a major issue. Since the WO3 lms have been found clearly behave as a n-type semiconductor [18,2224], then the crystallinity of WO3 lms should not be discarded. Semiconductor [18,2224] and conduction studies [25] on bulk WO3 have shown it to be oxygen decient. If it is assumed that vacancies act as dopants (oxygen vacancies imparting n-type character and cation vacancies p-type character), then oxygen vacancies are considered to be electron donors. However, it can be other kinds of defect-charge compensation different from the Schottky-type defect occur in solid oxides (e.g., low-valency cations, [26], surface states [2729], a non-uniform distribution of charge carriers and dielectric relaxation phenomena [27], among others). In this study, the diffusivity is considered to be that for the combination of these point defects, and the VO

where CO (0) is the concentration of oxygen vacancies at the lm/solution interface, CO (Lss ) the concentration of oxygen vacancies, at the metal/lm interface, a is the half-jump distance. Eq. (3) has two limit cases: the high-eld limit, zFaE0 /RT 1 and the low-eld limit zFaE0 /RT 1. Considering that in almost all cases Lss a, it is obtained that: At high-eld limit: CO (Lss ) = CO (0) exp Lss a zFaE0 2aJO exp DO RT (4) And at low-eld limit: CO (Lss ) = CO (0) exp zFE0 Lss RT RTJO DO zFE0 (5)

Comparing Eq. (1) with Eq. (4) and (5) and solving for DO , it is found that:

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At high-eld limit: DO = 2aJO zFaE0 exp w2 RT (6)

capacitance, Rsc and Lsc are associated to the surface charge at the lm/solution interface. Rb = Rsc 1 (9)

And at low-eld limit: DO RTJO = w2 zFE0 (7)

where R is the universal gas constant, T the temperature (K), F the Faradays constant, a the half-jump distance and z is the charge of the anionic vacancy. Considering the current is mainly due to the ux of oxygen vacancies, then JO = iss /2e, where iss is the steady-state current density and e is the charge of the electron. The value of DO can be calculated with Eq. (2), which is identical to Eq. (7) (at the low-eld limit). However, Eq. (6) (high-eld limit) will be used in this work in the calculation of DO , because the high limit approximation agrees with the supposition of the existence of a high electric eld within the oxide lm. 1.5. Calculation of E0 and w2 The value of E0 can be calculated from Eq. (8) [16] using the slope of Lss versus Ef , but to get E0 , must be known Lss = 1 (1 )Ef + B. E0 (8)

The value of E0 is calculated by comparing Eq. (8) with the slope of the curve of Lss versus Ef (Lss is obtained from the capacitance measurements of the oxide lm). Finally, w2 can be found by tting ND versus Ef and comparing with Eq. (1). Then, in this work, a combination of the surface charge approach (at the high-eld limit), the MottSchottky analy sis, the PDM and the value of the half-jump distance 1.90 A (obtained from the literature [30,31]), has been used to calculate the DO of the WO3 lms. 2. Experimental procedure The working electrode is a W bar (Alfa&Aesar, 99.95% purity), embedded in Teon, where only the base of the cylinder ( = 6.3 mm) is exposed. The reference electrode is calomel (sce), in a Luggin probe. The counter electrode is a graphite bar. The potentiostat/galvanostat, E&GG, PAR, model 283, was used to apply potentials and a frequencies analyzer, Solartron, model IF 1260, for impedance measurements. The W electrode was polished with SiC sandpaper, 1200. Next, it was polished with alumina (0.05 m), until a mirror surface is obtained, then it was rinsed with deionized water; subsequently, it was placed in an ultrasonic bath for 5 min and rinsed again with deionized water. 2.1. The WO3 formation and EIS characterization The W electrode was placed in 0.1 M HClO4 (J.T. Baker, A.R.) aqueous solution, not bubbled with nitrogen. Then a formation potential (Ef ) was imposed for 1800 s, in order to form the oxide lm. The Ef was within the range of 2.07.0 V versus sce. The current response was monitored during the experiments. The characterization of the formed lms was done by EIS, with the following parameters: the impedance spectra were obtained at the same potential that they were formed; the amplitude of perturbation was 30 mV, the frequency range scanned was from 100 kHz to 10 mHz. The validity of EIS data was evaluated through the analysis of error distribution of the real and imaginary impedance components. The random distribution of errors obtained in the data tting indicates their consistency with KramersKronig transforms (see below). 2.2. Differential capacitance measurements The differential capacitance measurements were performed, at constant frequency (1 kHz), after the lm was formed. This frequency was selected from a previous study, where the capacitance of the oxide lm was measured at different frequencies, in the range 10 Hz to 10 kHz. The spectra were obtained with the following parameters: the initial potential was Ef , the nal 0.1 V. In order to avoid any variation of the lm thickness, the scan rate was 0.5 V/s and the amplitude of the ac perturbation

where is the polarizability of the oxide lm/solution interface and B is a constant related with the thickness of the lm at a formation potential of 0 V, it depends on pH, on the rate constants for lm formation at the metal/lm interface and lm dissolution at the lm/solution interface. The surface charge approach provides a way to calculate the value of , by means of Eq. (9) [15]. The values of Rb and Rsc are obtained from tting the EIS spectra using the equivalent electric circuit (Fig. 1) proposed by Bojinov [15]. The circuit contains: Rel which is the solution resistance; Cs associated to the Faradaic pseudocapacitance, Rb the resistance of the oxide lm, C is associated to the barrier lm

Fig. 1. Equivalent electric circuit (eec) used to simulate the impedance behavior of the WO3 lms, in 0.1 M HClO4 solution. Rel is the solution resistance; Cs associated to the Faradaic pseudocapacitance; Rb the resistance of the oxide lm; C the barrier lm capacitance; Rsc and Lsc are associated with the surface charge at the lm/solution interface [15].

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10 mV. The space charge capacitance was calculated assuming Csc = 1/(Zim ), where Zim is the imaginary component of impedance and is the angular frequency. 3. Results and discussion The oxide lms on W were formed applying Ef for 1800 s, during all the experiment the current density was monitored, it was observed that the current density diminished with the time until a constant value was reached (i.e. steady state). Fig. 2 shows the values of the current density at steady state (iss ) versus the Ef . Since iss is nearly constant, then d(ln iss )/dEf 0. The PDMs diagnostic criteria [11], proposes that the interfacial equilibrium is governed by anion transmission on passive lms, when: d(ln iss )/dEf = 0 and = , where is the oxidation state of the metal atom in the oxide net, and is the oxidation state of the dissolved metal atom. Presumably, the dissolution product of W is the WO2 2+ cation, in very acid solutions, and the tungstate ion (WO4 2 ) in solutions with higher pH [32]. The oxidation state in the oxide lm is VI [32], and is also VI when it is dissolved, thus satisfying the condition = . Therefore, according to the PDM, it can be concluded that the interfacial equilibrium for the system, is governed by anion transmission, attributed to the transport of the VO (oxygen vacancies) through the lm, this fact is in agreement with the assumption that the dominant point defects in the oxide lm are the oxygen vacancies. 3.1. EIS spectra of the WO3 lms The impedance spectra of the WO3 in 0.1 M HClO4 are shown in Fig. 3. From the spectra, it could be seen that the impedance of the WO3 lms depends on Ef . The spectra comprise attened semicircles, with an inductive loop at middle to low frequencies. The attened semicircles indicate the existence of at least two time constants. This requirement is satised by the circuit in Fig. 1. The impedance spectra for the Ef s of: 2.0, 3.0, 4.0, 5.0, 6.0 and 7.0 V/sce, were tted using the program Boukamp [33]. The typical random distribution of errors (Fig. 4) obtained in the data tting spectra indicates their consistency with the

Fig. 3. Nyquist diagrams of the WO3 lms, previously formed in the 0.1 M HClO4 solution, at different formation voltages Ef , within the range from 2.0 to 7.0 V, indicated in the gure. The spectra in symbols represent the spectra experimentally obtained. The spectra in lines belong to the calculated spectra using the tting values of the boukamp program and the eec in Fig. 1.

KramersKronig transforms. This distribution is similar for the spectra of Fig. 3. The capacitance Cb has been calculated according to Eq. (10). The complete set of tted results is shown on Table 1. 1 1 1 + = Cb CH C (10)

where C is the capacitance value evaluated from the t of EIS spectra, Cb the capacitance of the oxide lm and CH is the Helmholtz layer capacitance which is assumed to have a constant value of 20 F cm2 [34]. 3.2. Analysis of Table 1 The oxide lm resistance (Rb ) increases as the Ef is greater, this could be due to the fact that the lm thickness is increased with the Ef . The oxide lm capacitance is inversely related to the lm thickness, since the lm thickness is expected to increase with the Ef , then Cb diminishes with the increment of Ef . Rsc and Lsc are associated with the surface charge at the lm/solution interface.

Fig. 2. Steady-state current density (iss ) obtained during the potentiostatic grown of the WO3 lms, at different formation potential Ef in 0.1 M HClO4 solution.

Fig. 4. Typical error distribution of the real and imaginary components of the impedance spectra, of the WO3 lms, formed in the 0.1 M HClO4 solution, at different formation voltages Ef , within the range from 2.0 to 7.0 V. The random distribution of errors obtained in the data tting (for lm grown at 4.0 V) indicates their consistency with KramersKronig transforms.

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Table 1 Values of the elements of the electrical circuit (Fig. 1), obtained by tting the corresponding transfer function and experimental data, of the impedance spectra of WO3 lms, in a 0.1 M HClO4 aqueous solution Ef (V) 2.0 3.0 4.0 5.0 6.0 7.0 Rel = 7 ohm cm2 . Cs (F cm2 ) 1.70 103 1.40 103 1.20 103 1.15 103 1.11 103 1.05 103 Rb (ohm cm2 ) 1.83 104 2.48 104 3.24 104 3.90 104 4.80 104 5.15 104 Cb (F cm2 ) 6.07 106 4.92 106 4.23 106 3.75 106 3.43 106 3.33 106 Rsc (ohm cm2 ) 6.79 104 7.96 104 8.90 104 10.00 104 12.11 104 12.50 104 Lsc (H cm2 ) 1.43 105 2.36 105 2.77 105 4.11 105 4.83 105 8.60 105

The value of can be calculated using Eq. (9), the values of the resistances Rb and Rsc are taken from Table 1. The value of has been averaged, in order to obtain a single value which may represent the polarization at the M/S interface, the average value of is 0.3, this value is smaller than the 0.5 value assumed by Sikora et al. [15], and that obtained by Bojinov (0.420.58) in sulphuric and phosphoric solutions with 1, 2 and 4 M [16]; nevertheless, the concentration in this work is very different (0.1 M). Macdonald et al. [35] obtained values for within the range of 0.20.8 for several metals (Fe, Ni, Cr, FeNi, FeCr) in borates and phosphates buffers. 3.3. Results of the MottSchottky analysis In this work, the differential capacitance measurements of the oxide lms were measured at high frequency (typically 1 kHz), immediately after the oxide lm was grown, at specic Ef . The MS plots were traced, assuming constant thickness of the oxide lm during the measurement and considering that Csc = 1/(Zim ) is valid. The typical behavior of the MS curves is shown in Fig. 5. Similar curves were obtained for the lms grown at different Ef . Fig. 5 shows two linear regions, one region is for Ec > 0.9 and the second for Ec < 0.9 V. This behavior has been observed for different media and metal oxides [16,36,37]. In Fig. 5, the measured capacitance at the range of 0.9 < Ec < 4 V, have other contributions different to the space charge capacitance, even Faradaic reactions in Ec near to Ef . Meanwhile, the Faradaic reaction is not present for Ec < 0.9 V, then the

impedance response is only capacitive, attributed to the space charge capacitance. The curve in Fig. 5, clearly shows an n-type semiconductor behavior of the oxide lm, which is expected for a material doped with electron donors (VO ), then the ND and the Efb can be estimated using the MS relationship, in Eq. (11), in the region of Ec < 0.9 V. 1 2 NA = 2 Csc ND Fr 0 E Efb RT F (11)

where NA is the Avogrados number (6.02 1023 1/mol), ND the density of donors, F the Faraday constant (9.65 104 C/mol), r the relative permittivity (43 in perchloric acid [38]), 0 the permittivity of vacuum (8.8542 1012 F/m), E the applied potential, Efb the at band potential, R the constant of the gases (8.314 J/K mol) and T is temperature (K) (298 K). The values of ND estimated using Eq. (11) are shown in Fig. 6 (the values of ND are in the same order of magnitude as those obtained by Sikora et al. [16]) and that obtained by Biaggio et al. [38]. In Fig. 6 it is observed that the ND diminishes exponentially as the Ef increases, the t of data in Fig. 6 with Eq. (1) was performed, and Eq. (12) represents the best t of the curve in Fig. 6. ND = 5.7 1018 + 2.1 1020 e0.4204Ef (12)

when Ef = 0 in Eq. (12) and ND is 2.16 1020 cm3 . This value is smaller than that obtained (ND = 3.2 1020 cm3 ) by Sikora et al. [16] in 1 M H3 PO4 and that obtained by Biaggio et al. [38]

Fig. 5. Typical behavior of the space charge capacitance Csc of the WO3 lms, after 1800 s of growth at Ef = 4.0 V, in 0.1 M HClO4 , with the applied potential (Ec ) varied at 0.5 V/s. The Csc was evaluated assuming Csc = 1/(Zim ). The dashed line represents the MS interval of the tting with Eq. (11).

Fig. 6. Variation of density of donors (ND ) of the WO3 lms, previously grown for 1800 s, in 0.1 M HClO4 at different lm formation potentials (Ef ). The dashed line is the tted curve given by the equation showed in the gure.

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3.5. The half-jump distance (a) Since a very small variation in the value of a have a great impact in the calculation of DO , then it is very important to have an accurate value of a, and to use a as known parameter in the calculation of DO . In this work, a is obtained from data reported in the literature. Kuzmin et al. [30] reported a study of the local environment around tungsten ions for the a-WO3 (amorphous-WO3 ), with different values of N (coordination number), which is an averaged value of the number of neighbors around the tungsten ions. Using EXAFS and XDR and performing a tting procedure, the coordination number and the DebyeWaller factors were obtained, with them the lattice constant a was calculated, the In the other hand, Hjelm et al. [31] obtained value is 1.9 A. reported that the lattice parameter for m-WO3 (monoclinic-WO3 is the most stable form of WO3 at room temperature) is 3.78 A, and then a 1.89 A. The MS analysis is valid for crystalline or (micro)crystalline oxide lms and would vary if they are amorphous. Investigations using MS plots, have found WO3 lms to behave as a n-type semiconductor [16,3739], which found the ND to be in the order of 101920 , proving to have reproducibility. Considering that the dispersion in the capacitance of the WO3 lms is due to: (i) the roughness of the lm and (ii) the probably existence of a synergic effect due to the non-uniform distribution of charge carriers, low-valency cations, dielectric relaxation phenomena, among others mentioned before. The crystalline or microcrystalline nature of the WO3 is taken into account. This consideration is important because the transport number and conduction mechanism in the growth of the oxide lms could vary between amorphous and crystalline. Then, considering the crystallinity of WO3 , the density of donors can be calculated by MS; the evaluation of DO could be performed the calculated by means of Eq. (6) (taking a equal to 1.9 A), value for DO is 3 1017 cm2 /s (as an example to see the importance of the parameter a, if the value of a was taken then DO would be 7 1019 cm2 /s, to be equal to 2.7 A, which is 100 times smaller than the calculated with a = 1.9 A). Table 2 shows the parameters calculated in this work to obtain DO with Eq. (6), the DO was calculated to be 3 1017 cm2 /s, which is 2 orders of magnitude smaller than the value obtained by Eq. (7) (using the low-eld limit 1015 ); and it is 1 order of magnitude greater than the value obtained with the surface charge approach [15], where in the half-jump distance values are in the range of 1.82.5 A, the calculation of DO .

Fig. 7. Variation of the inverse of the barrier lm capacitance (1/Cb ), of the WO3 lms, previously grown for 1800 s, in 0.1 M HClO4 at different Ef .

(1.1 1022 cm3 ), nevertheless, the media and/or concentration are different than the used in this work. The value of w2 can be obtained by comparing Eq. (12) with Eq. (1), the value obtained in this way is 5.7 1018 cm3 . The value of w2 used in the previous study of the semiconductor properties of WO3 by the surface charge approach [15] was taken from Sikora et al.s work [16]. 3.4. Film thickness The behavior of 1/Cb versus Ef (Fig. 7) has a linear relationship (except the point at 7 V, indicating a possible charge saturation at this potential). The linear relationship of 1/Cb can be correlated with the thickness of the oxide lm, taking Lss = r 0 /Cb , which corresponds to the relationship of a parallel plate capacitor. The values of Lss as function of Ef are shown in Fig. 8. Fig. 8 shows that the lm thickness increases as the Ef is increased, the comparison of the slope of the curve in the Lss versus Ef graph, with Eq. (8), gives the value of E0 (5.9 106 V/cm). This value agrees with the assumption of the high eld strength within the oxide lm, the value is similar to those reported by other authors, for different oxides and electrolytic media [16,34,39].

Table 2 Calculated parameters to obtain the DO of the WO3 lms Fig. 8. Variation of the thickness of the WO3 lms (Lss ), grown for 1800 s, in 0.1 M HClO4 with different Ef . The Lss was calculated from the values of the oxide lm capacitance (Cb ), the equation of the linear regression is shown (dashed line) in the gure. iss E0 w2 8.2 106 A/cm2 0.3 5.9 106 V/cm 5.7 1018 1/cm3

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4. Conclusions By means of the table from the PDM, for diagnostic criteria, it was concluded that the interfacial equilibrium due the transport vacancies within the WO3 lm is governed by anion transmission, attributed to the transport of the VO (oxygen vacancies) through the lm, this fact is in agreement with the assumption that the dominant point defect in the oxide lm are the oxygen vacancies (majority carriers). The obtained values of ND are in the order of 101920 , it was found that ND depends exponentially with the Ef , the ND values are similar to those obtained by Sikora et al. Additionally, the value of was calculated using Eq. (9), the average value for was 0.3, this value is smaller than that obtained by other authors; nevertheless, the concentration of the acidic solution, in this work is very different (0.1 M). 1/Cb allows calculating the thickness of the lm, which is function of the Ef . With the slope of Lss versus Ef the value of E0 (5.9 106 V/cm) was obtained, the values are in agreement with the assumption of the existence of the high eld strength the within the oxide lm. On the other hand, taking a 1.9 A, diffusivity of the anion vacancies was calculated, the value of DO was 3 1017 cm2 /s, which is at least 2 orders of magnitude smaller than the value obtained by Eq. (7) (using the low-eld limit 1015 ); and it is 1 order of magnitude greater than that obtained by the surface charge approach, the difference in the values of the diffusivities is attributed either to the variation of the half-jump distance values evaluated in the range of 1.82.5 A. Acknowledgements This work has been carried out with the nancial aid, from CONACYT (SEP-2004-C01-47162). G. V azquez is grateful to CONACyT for the postgraduate grant. References
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