The Role of Cu(I) in the Process of Forming Cu_2–xS Coatings by a Chemical Route

SUMMARY

The interaction of the Cu₂O adsorbed with Na₂S_n (n = 1–4), during formation of the Cu_2–xS coatings has been investigated by cyclic voltammetry.

The summarized reaction of this process has been shown to correspond to the equation:

Na₂S_n + Cu₂O_ad + H₂0 → Cu₂S_ad + (n–1)S^o + 2NaOH,

where S^o/Cu=(n–1)/2. Such a stoichiometry of reaction can be explained by the formation of an intermediate—the adsorbed polysulphide of Cu(I)—and by its subsequent decomposition into Cu₂S and S^o.

When a thicker coating is being formed, i.e., when the surface being coated is repeatedly immersed into an ammoniate solution of Cu(I) and S^o fully bounded:

S^o_ad + 2 Cu⁺ → CuS + Cu²⁺.

At the same time due to different solubility products (L=2.5·10⁻⁴⁸ and 6.3·10⁻³⁶ for Cu₂S and CuS respectively), an exchange

CuS_ad + 2(1–x)Cu⁺ → Cu_2–xS_ad+ (1–x)Cu²+ occurs.

After formation of Cu²⁺, parallel processes characteristic for the interaction of Cu(II) with Na₂S_n start to take place, during which S^o is also formed.

Keywords:

• Cu_2–xS coatings
• copper polysulphide
• elemental sulphur