Multi-method Analysis of the Metal/Electrolyte Interface: Scanning Force Microscopy (SFM), Quartz Microbalance Measurements (QMB), Fourier Transform Infrared Spectroscopy (FTIR) and Grazing Incidence X-ray Diffractometry (GIXD) at a Polycrystalline Copper Electrode

Abstract

The successful application of various in situ and ex situ analytical techniques has been demonstrated at the buried interface between a metal and an electrolyte. Scanning force microscopy (SFM), electrochemical quartz microbalance measurements (EQMB), grazing incidence x‐ray diffractometry (GIXD), Fourier transform infrared spectroscopy (FTIR) in the specular reflection absorption mode and electrochemical charge measurements proved complementary in the characterization of a polycrystalline copper electrode in alkaline 0.1 M sulphate, perchlorate, fluoride and chloride electrolyte contact at pH 12. The surface exhibited a mixture of Cu(111) and Cu(200) grains of the order of 100 nm. Repeated potential scanning in the double layer and passive oxide region, between ‐1.4 and +0.1 VMSE, resulted in a complete reorganization of the surface morphology but no detectable corrosion. The electrochemical exchange of H2O and OH− between the electrolyte and the oxide film took place reversibly in accordance with a solid‐state growth mechanism. The copper atoms were redeposited at crystallographically preferred sites, generating comparatively homogeneously oriented, narrow Cu(111)‐edged grain ridges of length 200 nm. In the Cu(I) potential range, the formation of several monolayers of amorphous Cu2O could be confirmed. Only after extended time periods in the Cu(II) oxide potential region, Cu2O recrystallized to a (111) phase accompanied by Cu2O(200) and Cu2O(110). In this region, one observed the formation of amorphous Cu(OH)2 concurrent with further growth of Cu2O. Strong CuOH IR stretching bands excluded the existence of CuO. At corrosive potentials of +0.25 VMSE, high anodic currents and substantial mass losses led to an electropolished surface with isolated features of <300 nm width and <70 nm height.© 1997 John Wiley & Sons, Ltd.

Electropotential-stimulated wear of copper during chemical mechanical planarization

“…In the case of electropolishing, previous research has shown that if current is reversed between anodic and cathodic potentials, the surface is smooth [17]. In this case, material removal rates could be negligible.…”

Electrochemical and Passive Behaviors of Pure Copper Fabricated by Accumulative Roll-Bonding (ARB) Process

“…Studies on the copper oxide passive films using different characterization methods have revealed that the composition of the copper oxide passive films depends on many variables such as solution conditions (Ref [17][18][19].…”

“…Although many studies have been published on the passive behavior of copper and its alloys (Ref [14][15][16][17][18][19], there is still lack of knowledge on the effect of ARB process on the passive behavior of the oxide film formed on copper and its alloys. Indeed, the microstructure which is also influenced by the forming process can affect the passive film formation and its behavior.…”

Electrochemical Behavior and Passivation of Cu–30Zn Alloy in Aqueous NaOH Solutions

“…Indeed, this passive film forms B Arash Fattah-Alhosseini a.fattah@basu.ac.ir 1 Department of Materials Engineering, Bu-Ali Sina University, Hamedan 65178-38695, Iran an efficient barrier against the metal dissolution. During the last decade, the composition of the passive films has been studied by using different surface characterization analysis [6][7][8][9]. However, the extensive number of researches has been focused on the passivation behavior of copper and its alloys [1][2][3][4][5][6][7][8][9][10], little paper has been published on the semiconducting behavior of the passive films formed on these alloys [10].…”

“…A large number of studies have already been reported to explain the properties and mechanism of the passive films on copper and its alloys [1][2][3][4][5][6][7][8][9][10]. However, little information about the effect of pH on the semiconductive behavior of the passive film formed on brass alloys was available.…”