On the origin of the spontaneous potential oscillations observed during galvanostatic deposition of layers of Cu and Cu2O in alkaline citrate solutions

Potential oscillations are demonstrated under reducing galvanostatic conditions in alkaline solutions of 0.4 M Cu(II) and 1.2 M citrate at elevated temperatures. The oscillations, which give rise to the deposition of layers of Cu and Cu2O, as verified by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) as well as Raman measurements, originate from local modulations of the pH in the vicinity of the working electrode. A reaction scheme for the oscillations is presented based on the model previously proposed by Leopold et al. [J. Electroanal. Chem., 547 (2003) 45-52] for the Cu(II)-lactate system. It is shown that the oscillations are due to the fact that the rate of the electrodeposition Of Cu2O is modulated by the local pH variations. This causes this reaction to be switched on and off as the local pH increases and decreases, respectively. In analogy with the Cu(II)-lactate case, a local pH increase is obtained during the deposition of copper from the [Cu(2)H(-2)Cit(2)](4-) complex ([Cu(2)H(-2)Cit(2)](4-) + 4e(-) + 2H(2)O = 2Cu + 2[Cit](3-) + 2OH(-)) predominating in the solution. This increase stems from the protonation of the liberated citrate. As a result of this, electrodeposition Of Cu2O ([Cu(2)H(-2)Cit(2)](4-) + 2e(-) + H2O = Cu2O + 2[Cit](3-)) becomes possible at the rate required by the constant current. However, electrochemical quartz crystal microbalance (EQCM) data clearly show that the onset of this reaction is accompanied by an electroless deposition of Cu2O. This reaction, which under oscillating conditions mainly involves a comproportionation reaction ([Cu(2)H(-2)Cit(2),](4-) + 2Cu + 2OH(-) = 2Cu(2)O + 2[Cit](3-)), can give rise to Cu2O deposition at current efficiencies much larger than 100%. As a result of the combined electroless deposition and electrodeposition Of Cu2O, the local pH decreases rapidly, mainly due to the comproportionation reaction. When the local pH drops, the electrodeposition Of Cu2O becomes unable to sustain the current and the potential shifts negatively. This causes the onset of the reduction of the previously deposited Cu2O (i.e. Cu2O + 2e(-) + H2O = 2Cu + 2OH(-)). The EQCM and XRD results, however, clearly show that this reduction is incomplete during the oscillating conditions. This finding, which explains the presence of both copper and Cu2O in the deposits, is ascribed to the formation of a growing layer of copper on top of the remaining Cu2O. It is shown that the extent of the Cu2O reduction (and thus the amount Of Cu2O in the obtained deposits) depends on the Cu(II) concentration in the solution. Finally, the oscillation cycle is completed by a gradual replacement of the reduction Of Cu2O by the reduction of the [Cu(2)H(-2)Cit(2)](4-) complex, which causes the local pH to increase again. The proposed model is discussed in detail with particular emphasis on the reactions taking place in the region of the oscillation potential peak. The requirements for the attainment of oscillations under quiescent and forced convection conditions are discussed as well as the applicability of the model with respect to other Cu(II)complx systems. (c) 2006 Elsevier B.V. All rights reserved.