Abstract
Electrodeposition of Cu-Ag films from acidic sulfate bath was conducted at n-Si(001) and polycrystalline Ru substrates. Significant nucleation overpotential of 0.4 V is observed with the Cu-Ag bath at n-Si(001) substrate, whereas the electrodeposition of Cu-Ag at Ru substrate is influenced by Ru oxides at the surface. Incomplete coverage of Si substrate by Cu-Ag deposit was observed from the deposition systems without Ag(I), or with 0.1 mM Ag(I), comparing with the compact Cu-Ag film obtained with the deposition bath containing 0.01 mM Ag(I). Layered and faceted Cu-Ag deposit was observed at small Cu deposition overpotential with the Ru substrate. Phase composition of the Cu-Ag deposits at n-Si(001) substrate from electrolyte with various Ag(I) concentrations is examined by XRD. Limited solubility of Ag (0.4 at.%) was observed in fcc-Cu until phase separation occurs. The classical model for nucleation kinetics in electrodeposition was used to examine the potentiostatic transients of the Cu-Ag electrodeposition at n-Si(001) substrate.
Highlights
IntroductionCharacterized by its complete immiscibility at room temperature [1], the Ag-Cu alloys have been used in fields such as bactericides [2], decorative artifacts (depletion gilding) [3,4], electrocatalysis (H2O2 reduction [5], ammonia oxidation [6], and CO as well CO2 reduction [7,8,9,10]), electrical contacts (interconnects [11], flexible electronics [12] and conductive inks [13]), sensors (electrochemical [14,15] or based on localized surface plasmon resonance [16,17,18,19]), usually in the form of nano-particles or core-shell nanowires
Characterized by its complete immiscibility at room temperature [1], the Ag-Cu alloys have been used in fields such as bactericides [2], decorative artifacts [3,4], electrocatalysis (H2O2 reduction [5], ammonia oxidation [6], and CO as well CO2 reduction [7,8,9,10]), electrical contacts, sensors, usually in the form of nano-particles or core-shell nanowires
Morphology of the deposit are usually aiming for the nanoparticles or dendrites [5,9,10,18,19,25,26], while smooth Cu-Ag thin films were achieved at low electrodeposition rates [25,29]
Summary
Characterized by its complete immiscibility at room temperature [1], the Ag-Cu alloys have been used in fields such as bactericides [2], decorative artifacts (depletion gilding) [3,4], electrocatalysis (H2O2 reduction [5], ammonia oxidation [6], and CO as well CO2 reduction [7,8,9,10]), electrical contacts (interconnects [11], flexible electronics [12] and conductive inks [13]), sensors (electrochemical [14,15] or based on localized surface plasmon resonance [16,17,18,19]), usually in the form of nano-particles or core-shell nanowires. To the best of our knowledge, the Cu-Ag alloys have been synthesized using electron beam co-evaporation [1,20], magnetron sputtering [21], co-incipient wetness and coimpregnation [6,14], direct mixing of nanoparticles, mechanical alloying [22,23], laser ablation and irradiation [16,17], Cu electrodeposition followed by galvanic replacement with Ag [5,7,12], and electroless deposition [2,13,15,24]. It is worth noting that due to complete immiscibility of Cu-Ag at room temperature, unlike alloy electrodeposition system with complete miscibility (e.g., Au-Ag [31,32,33]), underpotential codeposition does not occur in the Cu-Ag electrodeposition system
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