• Journal of the Korean Chemical Society
• /
• v.60 no.3
• /
• pp.169-176
• /
• 2016

In a borate buffer solution, the growth kinetics and the electronic properties of passive film on aluminum were investigated, using the potentiodynamic method, chronoamperometry, and multi-frequency electrochemical impedance spectroscopy. The corrosion of aluminum was heavily influenced by the degree of oxygen concentration because of the increasing reduction current. The oxide film formed during the passivation process of aluminum has showed the electronic properties of n-type semiconductor, which follow from the Mott-Schottky equation. It was found out that the passive film (Al(OH)₃) of Al formed in the low electrode potential changes to Al₂O₃ while the electrode potential increases. The growth kinetics data as measured by chronoamperometry suggests a mechanism in which the growth of the film of Al₂O₃ is determined by field-assisted transport of ions through the film.

• Journal of the Korean Electrochemical Society
• /
• v.12 no.3
• /
• pp.258-262
• /
• 2009

The composition and semiconducting properties of the passive films formed on Ni- (15, 30)Cr-5Mo alloys in pH 8.5 buffer solution were examined. The depth concentration profile of passive films formed on Ni-(15, 30)Cr-5Mo in pH 8.5 buffer solution showed that Mo enhances the enrichment of Cr. The Mott-Schottky plot for the passive film on Ni-(15, 30)Cr- 5Mo closely resembled that for the film on Cr, whereas those for the less Cr-enriched film on Mo-free alloys showed similar behavior to that for the film on Ni. The acceptor density was reduced by increasing Cr content in Ni-(15, 30)Cr-(0, 5)Mo alloys, but addition of Mo considerably increased the acceptor density.

• Corrosion Science and Technology
• /
• v.2 no.6
• /
• pp.253-259
• /
• 2003

Zirconium based alloys have been extensively used as a cladding material for fuel rods in nuclear reactors, due to their low thermal neutron absorption cross-section, excellent corrosion resistance and good mechanical properties at high temperatures. However, a cladding material for fuel rods in nuclear reactors was contact water during long time at high-temperature, so it is necessary to improve the wear and corrosion resistance of the fuel cladding, At ambient environment, there are few data or paper on the characteristic of corrosion in chloride solution and acidic solution. The specimens used in this work are pure Zr and Zircaloy-4. Zircaloy-4 is a specific zirconium-based alloy containing, on a weight percent basis, 1.4% Sn, 0.2% Fe, 0.1% Cr. Pitting corrosion resistance of two alloys by ASTM G48 is higher than that of electrochemical method. Passive film formed on Zircaloy-4 is mainly composed of $ZrO_2$, metallic Sn, and iron species regardless of formation environments. Also, passive film formed on Zr alloys shows n-type semiconductic property on the base of Mott-Schottky plot.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2015.08a
• /
• pp.243.2-243.2
• /
• 2015

We report a high-performing nanoscale NiO thin film grown by thermal oxidation of sputtered Ni film. The structural, physical, optical and electrical properties of nanoscale NiO were comprehensively investigated. A quality transparent heterojunction (NiO/ZnO) was formed by large-area applicable sputtering deposition method that has an extremely low saturation current of 0.1 nA. Considerable large rectification ratio of more than 1000 was obtained for transparent heterojunction device. Mott-Schottky analyses were applied to develop the interface of NiO and ZnO by establishing energy diagrams. Nanoscale NiO has the accepter carrier concentration of the order of 1018 cm-3. Nanoscale NiO Schottky junction device properties were comprehensively studied using room temperature impedance spectroscopy.

• Corrosion Science and Technology
• /
• v.2 no.5
• /
• pp.212-218
• /
• 2003

Electronic properties of passive films formed on Ti at film formation potentials $(E_f)V_{SCE}$ in pH 8.5 buffer solution and in an artificial seawater were examined through the photocurrent measurement and Mott-Schottky analysis. The passive films formed on Ti in pH 8.5 buffer solution exhibited a n-type semiconductor with a band gap energys $(E_g);E_g^{n=2}=3.4$ eV for nondirect electron transition, and $E_g^{n=0.5}=3.7$ eV for direct electron transition. These band gap values were almost same as those for the passive films formed in artificial seawater, indicating that chloride ion ($Cl^-$ in solution did not affect the electronic structure of the passive film on Ti. $E_g$ for passive films formed on Ti were found to be greater than those ($E_g^{n=0.5}=3.1$ eV, $E_g^{n=2}=3.4$) for a thermal oxide film formed on Ti in air at $400^{\circ}C$. The disorder energy of passive film, determined from the absorption tail of photocurrent spectrum, was much greater than that for the thermal oxide film farmed on Ti in air at $400^{\circ}C$. The greater $E_g$ and the higher disorder energy for the passive film compared with those for the thermal oxide fIlm suggest that the passive film on Ti exhibited more disorded structure than the thermal oxide film. The donor density (about $2.4{\times}10^{20}cm^{-3}$) for the passive film formed in artificial seawater was greater than that (about $20{\times}10^{20}cm^{-3}$) formed in pH 8.5 buffer solution, indicating that $Cl^-$ increased the donor density for the passive film on Ti.

• Corrosion Science and Technology
• /
• v.7 no.1
• /
• pp.40-44
• /
• 2008

Passive metal forms an interfacial diffuse layer on the surface of passive film by its reaction with $H^+$ or $OH^-$ ions in solution depending on solution pH. There is a critical pH, called pH point of iso-selectivity ($pH_{pis}$) at which the nature of the diffuse layer is changed from the anion-permeable at pH<$pH_{pis}$ to the cation-permeable at pH>$pH_{pis}$. The $pH_{pis}$ for a passivated Fe was determined by examining the effects of pH on the thickness of passive film and on the dissolution reaction occurring on the passive film under a gavanostatic reduction in borate-phosphate buffer solutions at various pH of 7~11. The steady-state thickness of passive film formed on Fe showed the maximum at pH 8.5~9, and further the nature of film dissolution reaction was changed from a reaction producing $Fe^{3+}$ ion at $pH\leq8.5$ to that producing $FeO_2{^-}$ at $pH\geq9$, suggesting that the $pH_{pis}$ of Fe is about pH 8.5~9. In addition, the passive film formed at pH 8.5~9, $pH_{pis}$, was found to be the most protective with the lowest defect density as confirmed by the Mott-Schottky analysis. Pitting potential was decreased with increasing $Cl^-$ concentration at $pH\leq8.5$ due probably to the formation of anion permeable diffuse layer, but it was almost constant at $pH\geq9$ irrespective of $Cl^-$ concentration due primarily to the formation of cation permeable diffuse layer on the film, confirming again that $pH_{pis}$ of Fe is 8.5~9.

• Journal of the Korea Institute of Information and Communication Engineering
• /
• v.10 no.9
• /
• pp.1663-1670
• /
• 2006

Single crystal Fe thin films were grown directly onto n-Si(111) substrates by pulsed electrodeposition. Cyclic Voltammogram(CV) indicated that the $Fe^{2+}/n-Si(111)$ interface shows a good diode behavior by forming a Schottky barrier. From Mott-Schottky (MS) relation, it is found that the flat-band potential of n-Si(111) substrate and equilibrium redox potential of $Fet^{2+}$ ions are -0.526V and -0.316V, respectively. The nucleation and growth kinetics at the initial reaction stages of Fe/n-Si(111) substraste was studied by current transients. Current transients measurements have indicated that the deposition process starts via instantaneous nucleation and 3D diffusion limited growth. After the more deposition, the deposition flux of Fe ions was saturated with increase of deposition time. from the as-deposited sample obtained using the potential pulse of 1.4V and 300Hz, it is found that Fe nuclei grows to three dimensional(3D) islands with the average size of about 100nm in early deposition stages. As the deposition time increases, the sizes of Fe nuclei increases progressively and by a coalescence of the nuclei, a continuous Fe films grow on the Si surface. In this case, the Fe films show a highly oriented columnar structure and x-ray diffraction patterns reveal that the phase ${\alpha}-Fe$ grows on the n-Si(111) substrates.

• Corrosion Science and Technology
• /
• v.2 no.4
• /
• pp.171-177
• /
• 2003

The electronic properties of the passive film formed on Fe-20Cr ferritic stainless steel in pH 8.5 buffer solution containing 0.05 M EDTA (ethylene diammine tetraacetic acid) were examined by the photocurrent measurements and Mott-Schottky analysis for the film. XPS depth profile for the film demonstrated that Cr content in the outermost layer of the passive film was higher in the solution with EDTA than that in the solution without EDTA, due to selective dissolution of Fe by EDTA. In the solution with EDTA, the passive film showed characteristics of an amorphous or highly disordered n-type semiconductor. The band gap energies of the passive film are estimated to be ~ 3.0 eV, irrespective of film formation potential from 0 to 700 $mV_SCE$ and of presence of EDTA. However, the donor density of the passive film formed in the solution with EDTA is much higher than that formed in the solution without EDTA, due to an increase in oxygen vacancy resulted from the dissolution of Fe-oxide in the outermost layer of the passive film. These results support the proposed model that the passive film formed on Fe-20Cr in pH 8.5 buffer solution mainly consists of Cr-substituted $\gamma$-$Fe_2O_3$.

• Corrosion Science and Technology
• /
• v.2 no.1
• /
• pp.7-11
• /
• 2003

Photoelectrochemical response and electrochemical impedance behavior was investigated for passive film formed on sputter-deposited Cr alloy in $0.1kmol{\cdot}m^{-3}$. Photoelectrochemical action spectrum could be separated into two components, which were considered to be derived from $Cr_2O_3$ ($E_g\sim3.6eV$) and $ Cr(OH)_3 $ ($E_g\sim2.5eV$). The band gap energy, $E_g$, of each component was almost constant for various applied potentials. polarization periods and alloying additives. The photoelectrochemical response showed negative photo current for most potentials in the passive region. Therefore, the photo current apparently exhibited p-typesemiconductor behavior. On the other hand, Mort-Schottky plot of the capacitance showed positive slope, which means that passive film formed on Cr alloy has n-type semiconductor property. These apparently conflicting results are rationally explained assuming that the passive film on Cr alloy formed in the acid solution has n-type semiconductor property with a fairly deep donor level in the band gap and forms an accumulation layer in the most of potential region in the passive state.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2016.02a
• /
• pp.401-401
• /
• 2016

Although vertically aligned one-dimensional (1D) structure has been considered as efficient forms for photoelectrode, development of efficient 1D nanostructured photocathode are still required. In this sense, we recently demonstrated a simple fabrication route for CuInS2 (CIS) nanorod arrays from aqueous solution by template-assisted growth-and-transfer method and their feasibility as a photoelectrode for water splitting. In this study, we further evaluated the photoelectrochemical properties surface-modified CIS nanorod arrays. Surface modification with CdS and ZnS was performed by successive ion layer adsorption and reaction (SILAR) method, which is well known as suitable technique for conformal coating throughout nanoporous structure. With surface modification of CdS and ZnS, both photoelectrochemical performance and stability of CuInS2 nanorod arrays were improved by shifting of the flat-band potential, which was analyzed both onset potential and Mott-schottky plot.