In situ AFM observations of oxide film formation o n Cu(111) and Cu (100) surfaces under aqueous alkaline solutions

Ikemiya, Norihito; Kubo, Toshikazu; Hara, Shigeta

doi:10.1016/0039-6028(94)00671-7

Cited by 91 publications

(72 citation statements)

References 17 publications

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“…To recognize these reactions, the voltammogram obtained on sintered alloy is compared with the voltammograms obtained on pure copper and silver ( Figure 5). The current peak A 1 is attributed to the adsorption of OH − and formation of the first oxide monolayer based on literal [10][11][12][13][14][15][16][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40] data to which, with different in situ techniques, the presence of absorbed hydroxyl ions on the surface of copper and silver in alkaline electrolytes is proved in the quoted area of potential. It is obvious that the current waves marked as A 2 and A 3 correspond to copper oxides formation.…”

Section: Resultsmentioning

confidence: 99%

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Electrochemical Behavior of Sintered CuAg4 at. pct Alloy

Rajčić-Vujasinović

Nestorovic

Grekulović

et al. 2010

Metall Mater Trans B

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MIRJANA RAJČ IĆ -VUJASINOVIĆ , SVETLANA NESTOROVIĆ , VESNA GREKULOVIĆ , IVANA MARKOVIĆ , and ZORAN STEVIĆ The electrochemical characteristics of sintered CuAg4 at. pct alloy in different stages of synthesis and thermomechanical treatment were examined by cyclic voltammetry in a NaOH medium. On the voltammograms recorded at the sintered alloy, six current waves can be noticed at the anodic part, and six corresponding current waves are observed at the cathodic part. A possible electrochemical reaction is attributed to each wave. The effect of the potential reversing limit was used to distinguish the correlation between the anodic and cathodic peaks. After the deformation with 60 pct deformation degree, the alloy becomes more corrosion resistant, whereas the corrosion mechanism remains the same as before mechanical treatment. Subsequent anneal of the deformed alloy at 533 K (260°C) for 150 minutes leads to the hardening effect. At the same time, the alloy remains corrosion stable, and some of the current waves present at the other voltammograms are hardly noticeable here. Also, we propose our own model of oxide layer formation on the surface of a Cu-Ag alloy.

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Section: Resultsmentioning

confidence: 99%

“…Many papers, both older and recent, discuss investigations of electrochemical oxidation of pure copper [10][11][12][13][14][15][16][17][18][19][20][21][22] or its alloys [23][24][25][26] in alkaline media. Pure silver is also investigated widely from the electrochemical point of view.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Behavior of Sintered CuAg4 at. pct Alloy

Rajčić-Vujasinović

Nestorovic

Grekulović

et al. 2010

Metall Mater Trans B

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“…The on-going trend of miniaturization towards the nanometer scale requires a more sophisticated understanding of the relevant interface properties of those devices containing such reactive materials as copper. An atomic scale understanding of copper corrosion phenomena, corrosion inhibition by organics [3][4][5][6], oxidation and precursor films for oxidation [7][8][9][10], anodic dissolution [11][12][13][14][15][16][17] and the formation of passive films [18,19] is thus of vital interest and has consequently been the focus of numerous fundamental studies. Since modern processing lines of chip fabrication also include ''wet'' chemical deposition processes the mastering of copper-electrolyte interfaces with or without potential control can be regarded as a particular challenge.…”

Section: Introductionmentioning

confidence: 99%

Copper dissolution in the presence of a binary 2D-compound: CuI on Cu(100)

2006

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Exposing a Cu(100) electrode surface to an acidic and iodide containing electrolyte (5 mM H 2 SO 4 /1 mM KI) leads to the formation of an electro-compressible/electro-decompressible c(p Â 2)-I adsorbate layer at potentials close to the onset of the copper dissolution reaction. An increase of mobile CuI monomers on-top of the iodide modified electrode surface causes the local CuI solubility product to be exceeded thereby giving rise to the nucleation and growth of a laterally well ordered 2D-CuI film at potentials below 3D-CuI bulk phase formation.Step edges serve as sources for the consumption of copper material upon compound formation leading to accelerated copper dissolution at the step edges. The 2D-CuI film exhibits symmetry properties and nearest neighbor spacings that are closely related to the (111) lattice of the crystalline CuI bulk phase. Intriguingly, the 2D-CuI film on Cu(100) does not act as an efficient passive layer. Copper dissolution proceeds at slightly higher potentials even in the presence of this binary 2D-compound via an inverse step flow mechanism. Further dissolution causes the nucleation and growth of 3D-CuI clusters on-top of the 2D-CuI film. This several nanometer thick 3D-CuI bulk phase passivates the electrode against further dissolution. Characteristically, the formation/dissolution of the 3D-CuI bulk phase reveals a significantly larger potential hysteresis of about DE = 320 mV while the appearance/disappearance of the 2D-CuI film is reversible with a potential hysteresis of only DE = 20 mV.

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“…In situ images of physically rather different electrochemical interfacial systems specifically in this AFM mode have been reported recently. These include: (a) Metal deposition and nanostructure formation and dissolution [12][13][14][15][16]; (b) electrochemical oxide and hydride growth at metal and semiconductor surfaces [17][18][19][20]; (c) anion adsorption [21,22]; (d) supramolecular organization of large nanometer-size adsorbate molecules [23,24]; and (e) synthesis and characterization of nanoscale metallic and semiconductor particles with microelectrode or other device-like properties [25,26]. Such investigations hold highly important perspectives for direct imaging of the surface morphology and its time evolution.…”

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confidence: 99%

A new cell design for potentiostatically controlled in situ atomic force microscopy

Madsen

Friis

Andersen

et al. 1998

Applied Physics A: Materials Science & Processing

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We describe the design and construction of a new type of AFM cell for in situ imaging under potentiostatic control. The cell is specifically designed for a Rasterscope 4000 TM AFM instrument with no need for instrumental modification, but can easily be adapted to other commercial instruments. The cell is a closed system with insignificant sample evaporation. It is a chemically and mechanically robust two-component system which enables fast assembly and testing prior to insertion and minimizes leakage problems. The cell is also laterally flexible, facilitating scanning of large areas, holds inlets for rapid flushing and change of solution, and contains an optical device for adjusting the laser beam deflection in aqueous and gas ambient environments.Cyclic voltammetry of a simple redox couple and combined cyclic voltammetry and in situ AFM of copper deposition/dissolution cycles testify to perfect cell performance.Atomic force microscopy (AFM) of nanoscale structure and dynamics at the interface between a solid and an aqueous solution has received broad recent attention in a range of contexts. In some cases the single most central issue is the natural aqueous medium for the systems addressed. This applies, for example to ionic crystal dissolution [1-3], surface chemical processes [4,5] and, conspicuously, to the imaging of proteins and of protein and protein-membrane complexes [6][7][8][9][10][11] in solution. Water is here both an integrated structural element of the molecules imaged and an absolute prerequisite for observation of the conformational changes and other dynamic features associated directly with protein function.AFM imaging of molecular structure and dynamics in aqueous solution could be assigned the appellation in situ AFM. This notion is, however, reserved for configurations where, in addition to the aqueous environment, potentiostatic substrate (and tip) control is required, i.e. for imaging of electrochemical interfaces. In situ images of physically rather different electrochemical interfacial systems specifically in this AFM mode have been reported recently. These include:a) Metal deposition and nanostructure formation and dissolution [12-16]; (b) electrochemical oxide and hydride growth at metal and semiconductor surfaces [17-20]; (c) anion adsorption [21, 22]; (d) supramolecular organization of large nanometer-size adsorbate molecules [23, 24]; and (e) synthesis and characterization of nanoscale metallic and semiconductor particles with microelectrode or other device-like properties [25, 26]. Such investigations hold highly important perspectives for direct imaging of the surface morphology and its time evolution. They are also complementary to in situ scanning tunneling microscopy (STM), where conductivity and electronic properties are primary observables rather than the outer system morphology, such as in AFM.In the present work we describe the design and function of a new type of AFM cell for in situ imaging under potentiostatic control. The cell is specifically designed to fit a commercial ...

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In situ AFM observations of oxide film formation o n Cu(111) and Cu (100) surfaces under aqueous alkaline solutions

Cited by 91 publications

References 17 publications

Electrochemical Behavior of Sintered CuAg4 at. pct Alloy

Electrochemical Behavior of Sintered CuAg4 at. pct Alloy

Copper dissolution in the presence of a binary 2D-compound: CuI on Cu(100)

A new cell design for potentiostatically controlled in situ atomic force microscopy

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