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Barrier and semiconducting properties of thin anodic films on chromium in an acid solution

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Abstract

The study of barrier and semiconducting properties of anodically formed oxide films on chromium in an acid solution was carried out using the Cr-quartz crystal electrode. The oxide film formation and growth occur through an anion vacancies transport via a low-field-assisted mechanism (H = 106 V cm−1). The anion diffusion coefficient, which quantitatively describes the transport of point defects within the growing film, was calculated from capacitance data using the Nernst-Planck equation for low-field limit approximation and Mott-Schottky analysis. The depletion region in the passive film, close to the film|electrolyte interface, dominates the semiconducting properties. The passive film on Cr in an acid solution behaves as an n-type semiconductor. An energy-band structure model of the passive film is given.

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Abbreviations

A :

Area of the electrode (cm2)

c :

Concentration (mol dm−3)

C :

Capacitance (F cm−2)

C SC :

Space charge capacitance (F cm−2)

CPE:

Constant phase element

D O :

Diffusivity of oxygen vacancies (cm2 s−1)

e :

Electron charge (1.602 × 10−19 C)

E :

Potential (V)

E f :

Film formation potential (V)

EC, EV:

Conduction (valence) band edge of semiconductor

E F :

Fermi level

E fb :

Flat-band potential of semiconductor (V)

f :

Frequency (Hz)

f c :

Characteristic frequency (Hz)

F :

Faraday constant (96,500 C mol−1)

H :

Electric field strength (V cm−1)

j :

Current density (A cm−2)

J O :

Steady state flux of oxygen vacancies (s−1 cm−2)

jω :

Complex variable for sinusoidal perturbations with ω =2fπ

k :

Boltzman constant (1.38 × 10−23 J K−1)

L ss :

Layer thickness (nm)

M i :

Molar mass of a species i (g mol−1)

N D :

Donor concentration (cm−3)

n :

Number of electrons interchanged

p :

Concentration of holes

Q :

Constant of the CPE (Ω−1 cm−2 sα)

Q :

Charge (C cm−2)

R :

Resistance (Ω cm2)

R el :

Solution resistance (Ω cm2)

T :

Temperature (°C)

t :

Time (s)

V :

Molar volume of the surface oxide (cm3 mol−1)

Z :

Electrode impedance (Ω cm2)

Z imag :

Imaginary part of the impedance (Ω cm2)

Z real :

Real part of the impedance (Ω cm2)

α:

CPE power

ε :

Dielectric constant of the film

ε o :

Dielectric constant of vacuum (8.85 × 10−14 F cm−1)

δ SC :

Space charge thickness (nm)

Δm :

Mass-change sensitivity (ng Hz−1)

γ :

Charge fraction

ω :

Angular frequency (Hz)

ν:

Scan rate (mV s−1)

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Acknowledgement

The financial support of the Ministry of Science, Education and Sports of the Republic of Croatia under the 125-0982904-2923 grant is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Electrochemistry, Faculty of Chemical Engineering and Technology, University of Zagreb, PO Box 177, 10000, Zagreb, Croatia

    Željka Petrović, Mirjana Metikoš-Huković & Ranko Babić

  2. Faculty of Mines and Metallurgy, University of Prishtina, MIP Trepca, 40000, Mitrovica, Republic of Kosova

    Nushe Lajçi

Authors
  1. Željka Petrović
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  2. Nushe Lajçi
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  3. Mirjana Metikoš-Huković
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  4. Ranko Babić
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Correspondence to Mirjana Metikoš-Huković.

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Petrović, Ž., Lajçi, N., Metikoš-Huković, M. et al. Barrier and semiconducting properties of thin anodic films on chromium in an acid solution. J Solid State Electrochem 15, 1201–1207 (2011). https://doi.org/10.1007/s10008-010-1192-8

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  • DOI: https://doi.org/10.1007/s10008-010-1192-8

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