Bismuth and Antimony Chalcogenides

In their pioneering work on the formation of photoelectrochemically active metal sulfides by oxidation of the parent metal electrode. Miller and Heller [29] reported the anodic formation of polycrystalline Bi2S3 on a bismuth metal electrode in a sodium polysulfide cell, wherein this electrode was used in situ as photoanode. When a Bi metal electrode is anodized in aqueous sulfide solutions a surface film is formed by the reaction 

Takahashi et al. [220] first reported the formation of Bi-Te alloy films with varying chemical composition by means of cathodic electrodeposition from aqueous nitric acid solutions (pH 1.0-0.7) containing Bi(N03)3 and Te02. The electrodeposition took place on Ti sheets at room temperature under diffusion-limited conditions for both components. In a subsequent work [221], it was noted that the use of the Bi-EDTA complex in the electrolyte would improve the results, since Bi is easily converted into the hydrolysis product, Bi(OH)3, a hydrous polymer, thus impairing the reproducibility of electrodeposition. The as-produced films were found to consist of mixtures of Te and several Bi-Te alloy compounds, such as Bi2Tc3, Bi2+xTe3 x, Bi Tee, and BiTe. Preparation of both n- and p-type Bi2Te3 was reported in this and related works [222]. 

The electrodeposition of Bi2Tes in typical acidic solutions can be described by the general reaction 

Cathodic deposition of bismuth(in) telluride films has been reported [224] also on copper and nickel foils, from aqueous nitric acid solutions of bismuth oxide and tellurium oxide in molar ratios of Bi Te = 3 3 and 4 3, at 298 K. The 

Electrodeposition of antimony sesquitelluride, Sb2Tc3, or of (Bii xSbx)2Te3 alloys from aqueous solutions is challenging because it is difficult to achieve a sufficiently high concentration of antimony. Complexing agents such as tartaric acid, citric acid, or FUTA have been used to solubilize Sb in water. 

---