Electrochimico

Pergamon 001~4686@4)00330-0

Acta. Vol. 40. No. 6. pp. 719-124, 1995 Copyright Q 1995 Elsevier Science Ltd. Printed in Great Britain. Allrightsrrscmd 0013-4686/95 S9.50 + 0.00

DIELECTRIC
0.

PROPERTIES OF ANODIC ON TANTALUM

OXIDE

FILMS

KERREC*, D. DEVILLIERS,~~ H. GROULT~ and M. CHEMLA~

*E.D.F. D.E.M. Centre de Recherche des Renardi&es, 77250 Moret sur Loing, France;

tuniversitb

P. et M. Curie, Laboratoire dElectrochimie, URA CNRS 430, 4 Place Jussieu, 75252 Paris Cedex 05, France (Received 6 June 1994; in revisedform 12 September 1994)

Abstract-The electrochemical behaviour of Ta-Tao, structures was investigated by impedance spectroscopy. It was shown that, after the polishing treatment, the electrode is covered by an initial oxide film containing tantalum monoxide, Tao, and that electrogenerated oxides are only composed of tantalum pentoxide, Ta,O, (297 mol%). However, the dielectric properties of the structures strongly depend on the thickness of the oxide, d_, because of the influence of a sub-stoichiometric oxide of TaO in thin layers, in agreement with previous results obtained by XPS measurements. The variation of the reciprocal total capacitance of the oxide, C,, with the quantity of electricity, Q,, involved in the formation of the oxide exhibits two linear parts. The breakdown of the slope of that curve is interpreted by a variation of the relative permittivity, E,, of the oxide with its thickness: for thin films (d,, < 19 nm), E, z 18.5 and for thick films (d,, > 19 nm) E, z 27.5. Key words: tantalum oxide, permittivity, anodic oxide films, impedance spectroscopy.

NOMENCLATURE
A B

ca
c
tin -P

ctl CO, cpe din 4 4

d ox

E E 4

F G I j L M
n nhe

P a R ra R, RS

surface area susceptance (imaginary part of admittance) capacitance capacitance of the anodic film total experimental capacitance Helmholtz capacitance capacitance of the initial oxide total capacitance of the oxide constant phase element thickness of the initial oxide thickness of the electrogenerated oxide critical thickness of oxide film total thickness of the oxide layer potential standard potential potential of the working electrode reached after a galvanostatic pulse Faraday constant conductance (real part of admittance) electric current current density inductance molar or atomic mass number of exchanged electrons normal hydrogen electrode characteristic parameter of a cpe quantity of electricity involved in the formation of the oxide resistance ratio of the slopes cc,/uz low-frequency resistance of the oxide layer electrolyte resistance

pseudo-capacitance of a cpe molar volume X mole fraction Z cpe impedance of a distributed element (cpe)
%?I Greek symbols a slope of

co E, Y 0
P

the curve: l/C,,, =f(Q,) permittivity of vacuum relative permittivity roughness factor angular frequency density constant phase angle of a cpe 1. INTRODUCTION

The study of the electronic and electrochemical properties of structures composed of a metallic substrate covered by an oxide film, called M.O. structures, presents a great fundamental and applied interest. Indeed, the insulating properties of the oxide can be used for protection against corrosion, capacitor manufacturing etc. Tantalum has been chosen for these experiments because this valve metal is reported to lead to the formation of a compact passivating oxide film of tantalum pentoxide, Ta,O, . The corresponding half-cell reaction is : Ta,O, + 10 H+ + 10 e-o2 Ta + 5 H,O vs. nhe.
(1)

E z -0.75V

$ Author to whom correspondence should be addressed. 719

If Ta-Ta,O, structures are used as electrodes in an electrolyte containing a redox couple Ox-Red, the presence of the oxide film constitutes an energy barrier which lowers significantly the kinetics of the electron transfer for the reaction Ox + ne- = Red.

120

0. KERREC et al

These structures also present a diode effect: anodic reactions are totally blocked[ I,23 and cathodic reactions can be observed if a sufficient overvoltage is applied. It has been shown that the anodic oxide film formed on a tantalum substrate grows linearly with increasing electrode potential by high-field ion migration in the film[3]. The oxide layers are generally non-stoichiometric and amorphous[3], and are subject to variations in permittivity, ionic and electronic conduction. Therefore, tantalum oxide will be denoted Tao, hereafter. The electrochemical behaviour of Ta-Tao, structures depends on the thickness of the oxide. Schultze and Macagno[l, 23 have shown that, for thin oxide layers (d,, < 15 nm) formed by potentiostatic polarization, a n-type semiconductor behaviour is observed; for thicker films, the structures are insulating. The variation of the charge carriers density, with the oxide thickness, has been proposed to explain-such a phenomenon[l, 41. A similar behaviour was observed recently by steady-state voltammetry, impedance spectroscopy and X-ray photoelectron spectroscopy experiments on Ta-Tao, structures prepared by galvanostatic oxidation[5]. XPS revealed the presence of substoichiometric oxides in thin layers of Tao,: the (II) and (V) oxidation states of tantalum were observed for d,, < 15 nm. Therefore, the chemical composition of thin tantalum oxide layers is heterogeneous: a tantalum monoxide film, Tao, is located between the metallic substrate and the outer Ta,O, layer. On the contrary, thick oxide films are mainly composed of tantalum pentoxide, Ta,O, , containing only a small amount of sub-oxides, ie not more than 3 mol%. The composition heterogeneities in thin films can partially explain why the electrochemical behaviour and the conduction properties are different for thin and thick oxide films. The purpose of this paper is to analyse the dielectric properties of the films from impedance spectroscopy measurements. It will be shown that the average permittivity, E,, of the electrogenerated oxides films varies with their total thickness, d,,, due to the influence of the sub-oxide Tao.

25C using an EG&G PAR model 273 generator. This treatment leads to electrogenerated oxides. The electronic properties of an oxide layer may be deduced by capacitance determination from galvanostatic E =f(t) curves[6]. However, more accurate values of capacitance were obtained using UCimpedance measurements. In this paper, a HewlettPackard 4192A frequence response analyzer driven by a Hewlett-Packard HP9816 computer was used for the UC impedance measurements in the 1 MHz5Hz frequency range. The amplitude of the sinusoidal signal was 5-20mV depending on the thickness of the oxide layer. A nul dc potential was applied between the working electrode (Ta-Tao3 and the large platinum counter electrode (A = 20cm*). The impedance of the total circuit is composed of the contribution of the electrolyte (H2S0, 0.5M) and that of the Ta-TaO,-electrolyte structure. The contribution of the counter electrode may be neglected. The Ta-Tao,-H,SO, structure can be described as a plane capacitor in which the tantalum substrate is the first armature, and the electrolyte the second armature. This structure may be schematically represented by an equivalent circuit composed of a resistance R, in series with an inductance L and a loop (cpe, RP) (Fig. 1). The term R, contains mainly the contribution of the electrolyte resistance. L is attributed to the inductance of the wires. This term cannot be neglected when large values of the frequency are used. The loop (cpe, RJ takes into account the dielectric properties of the passivating oxide layer. As the Nyquist diagrams, obtained in admittance representation, were not always perfect semi-circles because their centres were situated underneath the real axis, a cpe has been chosen instead of a pure capacitor. A cpe is a distributed element which cannot be represented by a combination of discrete elements R, L or C. It contains an infinite number of elementary loops, with time constants distributed around an average value. The impedance of a cpe can be described by the empirical equation[7, S] :
Zcpe = T-(i~0-~ (2)

2. EXPERIMENTAL All the experiments were performed with an electrode fitted with a pure tantalum disk (Goodfellow; purity: 99.9% ; A = 0.16 cm*). The samples were polished successively with JPS abrasive paper (silicon carbide; granulometry 3pm) and Buehler alumina suspensions (granulometry 1 and 0.3 pm), and rinsed with distilled water in an ultrasonic cleaner. Due to polishing treatment, the samples were covered by a thin layer of Tao, called initial oxide hereafter; its composition was different from that of native oxide, spontaneously formed on tantalum by exposure to the atmosphere (dry substoichiometric oxide). The roughness factor for polished tantalum electrodes is estimated to be in the range l-1.6[1, 63. For our experiments, we assume that y = 1.1. The oxidations were made with a constant current density j = 0.7 mA cm -, in 0.5 M sulphuric acid at

where i = (- 1). The exponent p (0 < p < 1) is related to the constant phase angle of the cpe in the complex plane: 8 = (1 - p)n/2. A cpe behaviour which reveals the capacitive dispersion can be attributed to the heterogeneities of the oxide composition revealed by XPS measurements[5]. Those heterogeneities result from the presence of: (i) tantalum monoxide, Tao, which creates energy levels different from those of Ta,O,; (ii) impurities, such as ionic species contained in the electrolyte solution and inserted into the film during the oxidation step. For example, it was shown, using nuclear reaction micro-

T, P

Fig. 1. Equivalent

circuit of a Ta-Tao,-H,SO,

structure.

Dielectric properties of anodic oxide films

103B/S
110

721

oxide, sandwiched between two conducting armatures, the capacitance is inversely proportional to the total thickness, d,, , of the dielectric as follows:

aox
p
tJ

Fig. 2. Nyquist plots for a Ta-Tao,-H,SO, structure. Admittance representation. B and G expressed in siemens (n-r). Oxide film prepared by a galvanostatic pulse,
j = 0.7mAcm-2; E, = 15.2V; experimental simulated curve (0). curve (+).

In fact, the total oxide thickness (Fig. 3), d,,, is composed of di,, thickness of the initial oxide present after the polishing step, and Z Ad resulting from the successive anodization steps. A linear variation of l/C,, with the total charge, Q, = I: AQ. is expected, according to the Faraday law. d,, is expressed as :
d,, = di, + Z Ad = di + nFAy

Q,K,

(4)

analysis, that 0.8-2.5% nitrogen per oxygen atom were present in anodic Ta,O, films, prepared in KNO,-containing solutions[9]. Impurities create localized states in the forbidden band. These inclusions induce a dispersion of the intrinsic polarisation properties of the oxide. The low-frequency resistance R, represents the leakage resistance of the dielectric. As very large values of R, are usually obtained with Ta-Tao, electrodes, a simplified circuit may be chosen, including three terms in series R,, L and a cpe.

l/C,, can also be written as the sum of two terms: l/Ci, and l/C,, with:

c,=nF&,

Q, Vi,
E,

A2y2

(5)

Experimental data were analysed with the LEVM complex non linear last-square fitting program developed by J. R. Macdonald (University of North Carolina, U.S.A.). A Nyquist diagram, in the admittance representation, obtained for E, = 15.2 V, is presented in Fig. 2. This figure shows that the simulated spectrum, using the equivalent circuit described above, is in very good agreement with the experimental data. 3. RESULTS
AND DISCUSSION with the oxide

because the capacitance of the electrogenerated oxide, C,, is in series with the capacitance of the initial oxide, Ci,, as it is described in Fig. 3. So, a linear variation of l/C,, with Q, is expected. The value of C,, may be calculated from Cexp, taking into account the influence of the Helmholtz capacitance, C, , according to :
1 _=-+_ c erfJ 1 Cm 1 C

(6)

3.1. Variation ofthe capacitance thickness

3.1.1. General model of oxide growth. In the case

of a plane

capacitor

comprising

one passivating
din

The value of C, commonly used in the literature is: 20pFcm-2[l]. The Cexp, C,,, Q, and E, values are reported in Table 1. The Ci, value was calculated from Ccrp when Q, = 0 (first line of Table 1). The curve l/C,, =f(Q,) is presented in Fig. 4. Two linear parts were observed. A critical thickness, denoted d,, corresponding to the breakdown of the slope, is obtained for Q. z 6.6 mC. The simple model described above cannot explain this phenomenon. For the understanding of this behaviour, the influd al d a,

CH

Gin

Ca 1

f&i 2

C exe Fig. 3. Model for the Ta-Tao,-H,SO,

structure.

722

0. KERREC et al.

Table 1. Results obtained with the LEVM fitting program from admittance data with initial oxide (first line) and electrogenerated oxides. Area of the electrode: A = 0.16cmz. dzX: thickness deduced from impedance measurements;
dz:: thickness deduced from the Faraday law

ErlV

2.0 7.5 12.3 15.2 17.7 25.0 32.8 42.3 52.0 70.2

QJmc 0.45 2.40 4.50 5.61 6.60 9.45 12.30 16.40 21.00 28.30

RP
4.6 4.5 4.5 4.1 4.7 4.4 4.6 4.6 4.5 4.5 4.7

C,,hF
2.241 0.827 0.298 0.181 0.151 0.123 0.098 0.086 0.068 0.058 0.040

Of
4.65 3.29 2.06 1.75 1.53 1.10 1.83 2.28 2.40 2.79 1.97

C,IPF
1.545 1.115 0.328 0.191 0.158 0.128 0.101 0.088 0.070 0.058 0.040

GfccF
1.308 0.343 0.196 0.161 0.130 0.102 0.089 0.070 0.059 0.040

c,,f~F
1.308 0.343 0.196 0.161 0.161 0.161 0.161 0.161 0.161 0.161

C.,fLtF
0.624 0.271 0.194 0.123 0.093 0.054

d,,/nm
2.2 8.4 14.7 17.9 17.9 17.9 17.9 17.9 17.9 17.9

d,,fnm
6.9 15.8 22.1 34.9 46.0 79.8

C&m
0.8 3.0 9.2 15.5 18.7 25.6 34.5 40.8 53.6 64.7 98.5

dZ::lnm
3.0 9.3 16.1 19.7 22.4 31.4 40.5 53.5 68.1 91.2

ence of the initial oxide and the composition of the electrogenerated oxide are studied hereafter. 3.1.2. Influence of the initial oxide layer. The influence of Ci, on the total capacitance must be considered especially for thin films. The variations of (Ci,,/C0x)-1 with Q. are presented in Fig. 5. The contribution of l/C, does not exceed 10% for Q, > 4mC. But it cannot explain the breakdown of the slope observed in Fig. 4. The influence of l/C,,, as well as the influence of l/C,, only give rise to a translation of all the experimental points towards lower values. 3.1.3. Influence of the oxide permittioity. An oxide layer 3 is characterized by three intrinsic param-

eters: V,, , E,,and n, . The presence of two linear parts in the curve l/C,, =f(Q.) may be interpreted by two different dielectric properties of the oxide, depending on its thickness. Let us consider rllr, the ratio al/a2 where aI and a2 are respectively the slopes of the two linear parts of the curve for thin and thick layers. This ratio is deduced from relation (5):

0; 0 10 20 30

Q, I

mC

The experimental value of r., deduced by linear regression, is m 1.5. XPS measurements have shown[S] that a thin native film of tantalum monoxide, Tao, is already present on the metallic substrate before polishing. After this treatment, an initial oxide, composed of 12 mol% of TaO and 88mol% of Ta20,, is present at the surface of the samples. In addition, electrogenerated oxides are composed of 97mol% of Ta,O, and only 3 mol% of Tao. However, the influence of the TaO sub-oxide may be important on the dielectric properties of thin films. Therefore, it may be considered that Ta,O, is the single of electrogenerated oxide. The molar volume of a compound is defined as follows: v,, =

Fig. 4. Variation of l/C,, for the Ta-Tao,-H,SO, structure vs. the quantity of electricity involved during the anodic formation, Q,

3
Pi

(8)

with: V,,, , = 53.9cm3m01- and V,, = 10.8 cm3 mole*. The value of pr.o is not mentioned in the literature. As the value of pNbo verifies the relation: pNblO, < pNbo < pNI, one can estimate that the same behaviour will be obtained with tantalum 8.2 < pTIO < 16.7gcmA3. By dividing this inequality by MTaO, one obtains, after inversion:
0

:I**
0

0,

,_

10

20
Q,!mC

12 < v,,
30

< 24cm3 mol-

(LO)

Fig. 5. Contribution of the Helmholtz capacitance, C,, and of the capacitance of the initial oxide, Cln, to the experimental capacitance, C,, . 0: (C&J; A: (Gl/c,.)- I.

The initial oxide contains the highest ratio of Tao. Its molar volume, V,,, may be estimated from :

44,.= k*,,, ho,

v,,

XT.0

(11)

Dielectric properties of anodic oxide films

723

with X,,,,,

= 0.88, XTIo = 0.12; thus 48.9 < I$, < 50.3 cm mol- 1 . (12)

3). The total capacitance relation (15):

1

of the oxide layer verifies

Although V,,, is not known with a good accuracy, the value of V,, is assumed to be: 49.6 f 0.7 cm3 mol- . The mean number of electrons involved in the formation reaction of the initial oxide is:
4, = +a205

C,,-

_i+
tin

cal

(15)

X TnzO5

%a0

X TaO

(13)

l if d,, > d, the anodic oxide is considered as two superposed layers, with two permittivities, E,, and E,~. The capacitance of the second layer is denoted C,, (Fig. 3) and the total capacitance of the oxide verifies relation (16):

with nTazO,= 10, nTaO= 2 and nin = 9.04. The ratio &,,n,/V,,n,, equal to _ 1.02, cannot explain the breakdown of the slope observed for the curve l/C, =f(Q.). Therefore, a variation of the dielectric constant must be taken into account in order to justify the experimental value of r.. The permittivity expresses the aptitude of polarisable species, as ions constitutive of the dielectric, to oscillate around their equilibrium position when a perturbation is applied. It depends on the nature of the material[lO]. Depending on the thickness of the oxide layer, two different values of E,~were obtained from the slopes a, and LYE: & r, = 18.5 for thin films (E, < 152V) E,~= 27.5 for thick films (E, > 15.2V). (14)

1 1 -_=-+-+-_. Cox tin

1
cal

1
ca*

(16)

The values of all these terms are reported in Table 1. 3.2. Determination of the oxide thickness 3.2.1. From the capacitance. Knowing the values of C,, and C,,, it is possible to determine the thickness of each layer within the frame of the model of the double dielectric layer described before. The total thickness of the oxide, d,, , is: do, = din + da, + da, with
d,, =e0wA G,

(17)

The latter value is roughly similar to the common value given in the literature for Ta,O, layers (x25)[2, 6, 111. For thin films, the value of E, is lower and can be compared with those obtained for some semiconductors[l2]. These interpretations, deduced from impedance data, are in agreement with previous results published by Schultze and Macagno. These authors have observed that Ta-Ta,O, structures present a semiconductor or insulating character depending on the oxide thickness[2]. Macagno and Schultze have shown that the charge carriers density decreases when the thickness of the layer increases[l]. Randall et aI.[l3], using the radio-tracers technique, have proved that incorporated species act as donor centres in the forbidden band of the oxide. These defects, incorporated into the oxide during its growing, can arise from the electrolyte; they act as electronic traps[l4, 15). The presence of the initial oxide seems to modify significantly the dielectric properties of the anodic layer until a critical thickness, d,, is reached. It corresponds to the breakdown of the slope of the curve l/C,, =f(Q,) but its effect is negligible on thicker layers. The influence of the preparation mode of the surface samples on the capacitances and the dielectric constant values has been mentioned by other authors[l6]. The different composition and charge carriers density can explain the variations of the permittivity (and probably of the ionic conductivity) with respect to the thickness. For Ta-Tao, structures, two models must be considered, depending on the oxide thickness : l if d,, < d, the anodic oxide layer may be considered as a single dielectric with a permittivity, E,,; the corresponding capacitance is denoted C,, (Fig.

for d,, < d,

(18)

and
eo ~2 YA d,, = -

for d,, > d,

(19)

The di, value (Table 1, first line) was calculated from the capacitance Ci, which was determined from an experiment performed with a freshly polished electrode, according to relation (20): 1 _=__tin

1
cexp

1
cH

As the value of C, is not well known and as its influence is significant for thin layers, the values of Ci, and di, are not very accurate. Moreover, the same value of E,~ was considered for the initial oxide and thin films (18.5); but, as the ratio of TaO is more important in initial oxide than in thin electrogenerated oxide layers[5], the permittivity of the initial oxide layer is probably lower than 18.5. For all these reasons, we prefer to choose the value of di, obtained from XPS measurements: di, z l.Snm[S]. 3.2.2. From the Faraday law. XPS measurements have shown that the thick layers of electrogenerated oxide are constituted by about 95 mol% of Ta,O, . Therefore, considering that the oxide is only composed of Ta,O, with a faradaic yield of lOO%, one can write, from relation (4) d,,(nm) = 1.5 + 3.17Q,(mC) . (21)

The d,, values calculated from this relation are reported in Table 1. As can be seen in Fig. 6, very good agreement is obtained between these values and those determined from impedance measurements considering two layers with different relative

124

0. KERREC et al.

Ef I

d,,

nm

Fig. 6. Variations of the potential of the working electrode

at the end of the galvanostatic pulse, E,, vs.the thickness of the layer, d,,, calculated from: the Faraday law (0);

impedance measurements (+).

dielectric constant. On the contrary, the values of d,, obtained from capacitance measurements, considering only a homogeneous layer of pure Ta,O, with E, = 233, 23, were significantly different and are not presented in Table 1. It can be concluded that the validity of the hypothesis of a faradaic yield of 100% is valid for a tantalum substrate. On the contrary, with other materials such as silicon[16] or titanium, a significant part of the current results in oxygen evolution. A linear variation of the potential reached by the working electrode at the end of the galvanostatic pulse, I$, with respect to the thickness layer, d,, , was observed. The slope of the curve E, =f(d,,,), calculated by linear regression, is 1.29 nm V- . This linear relationship is valid for the whole thickness range and allowed us to estimate the thickness of all electrogenerated tantalum oxide layers. The slope is lower than those given by other 1.67nmV-[ll] and authors : 1.76nmV-Cl], 1.57 nm V-[17], but the experimental conditions are different. For example, when experiments are performed with a galvanostatic technique, the slope depends on the current density and on the nature of the electrolyte. When the oxide layers are generated with potentiodynamic conditions[l], the linear relationship is E, =f(d,,), where E, is the formation potential. One can notice that our results were not different but complementary with previous ones. Indeed, other authors have studied either thicker layers of Ta,O,[l, 33 or performed different kinds of experiments such as the determination of the capacitance term using only one frequency for Mott-Schottky plots: l/C2 =f(E)[l, 21. Moreover, the kinetics of the oxide growth is strongly dependent on the preparation of the surface and on several parameters such as the nature, the concentration and the pH of the solution, the current density, the temperature and the electrochemical oxidation mode (galvanostatic or potentiostatic).

treatment, oxidation mode. The first oxidation steps play a very important role on the subsequent electrochemical behaviour of the interface (memory effect). Tantalum substrates are covered by a thin film of native oxide containing mainly tantalum monoxide, Tao. Mechanical polishing induces the formation of a mixed oxide composed of TaO and Ta,O, . When a galvanostatic pulse is imposed to the electrode, Ta,O, is the single electrogenerated oxide. The model of the double dielectric presented in this paper allows to calculate the thickness of the electrogenerated oxide from capacitance measurements. It has been shown that the TaO sub-oxide has an important influence on the relative permittivity, E,, of the films: for thin films (d,, d 19nm), E, = 18.5, for thick films, E, z 27.5. Nevertheless, the accuracy of the determination of E, strongly depends on the thickness of the layers because : (i) for d,, < 19 nm, the influence of TaO is important but the permittivity of TaO is not well known. The determination of d,, by XPS gives accurate results for thin films, but that technique is not easy to perform; (ii) in addition, for very thin layers (d,, < 3 nm), the influence of the Helmholtz capacitance is important. The value of Cu commonly mentioned in the literaturecl] has been taken into account; but it is possible that this value does not exactly correspond to our system.

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Electrochim. Acta 32,255 (1987).

4. CONCLUSION The nature of the outer layers of the TaO,-electrolyte interface depends strongly on its preparation : presence of native oxide, polishing

15. I. Montero, J. M. Albella, C. Ortega and J. Seijka, Thin

Solid Films 167,95 (1988).

16. H. J. Lewerenz, Electrochim. Acta 37, 847 (1992). 17. I. Montero, J. M. Albella and J. M. Martinez-Duart,
Electrochim. Acta 35,855 (1990).