Synthesis of CuSbS₂ Nanoplates and CuSbS₂–Cu₃SbS₄ Nanocomposite: Effect of Sulfur Source on Different Phase Formation

Abstract

Layered CuSbS2 and related ternary metal chalcogenides have attracted huge research interest due to their potential applications in sustainable energy storage, photovoltaics, and related area. Here, we report facile synthesis of CuSbS2 nanoplates and CuSbS2–Cu3SbS4 nanocomposite using hot injection method with varying sulfur precursors. Elemental sulfur (S8) as sulfur precursor results in nanoplates of pure CuSbS2, while thioacetamide (TA) as sulfur source gives nanocomposite with Cu3SbS4 nanoparticle decorated on the surface of CuSbS2 nanoplates. The ease of reduction of TA as compared to sulfur at high temperature, in the presence of oleylamine, promotes the oxidation of antimony from (III) to (V) state and the formation of Cu3SbS4 phase containing Sb­(V). Raman scattering study confirms the presence of Cu3SbS4 phase in CuSbS2–Cu3SbS4 nanocomposite. X-ray photoemission spectroscopy study on CuSbS2 nanoplates and CuSbS2–Cu3SbS4 nanocomposite confirms the desired valence state of the constituent elements. Electrochemical properties measurement shows better specific capacitance for CuSbS2–Cu3SbS4 nanocomposite (151 F/g) as compared to CuSbS2 nanoplates along with long-term cyclic stability with 68.2% capacitance retention.

Optoelectronic Effects of Chemical and Thermal Treatments on CuSbS2Nanocrystal Thin Films

“…2−13 Key characteristics supporting its potential as an alternative solar absorber include the following: (1) the scarcity and world demand for Sb is significantly lower than In, 1 (2) theoretical studies suggest that CuSbS 2 is free of deep trap recombination centers that plague Cu 2 ZnSnS 4 , another attractive, earth-abundant solar absorber material, 12 and (3) CuSbS 2 has a melting point of 551 °C, enabling lowtemperature crystallization, which is ideal for low-temperature, large-scale manufacturing. 12,13 The potential for CuSbS 2 as a solar absorber (as well as other semiconductor applications such as dye-sensitized solar cells, thermoelectrics, 14,15 supercapacitors, 2 and battery electrodes 16,17 ) has driven the development of many synthetic methods. Gas-phase (i.e., thermal evaporation, 11 low-temperature atomic layer deposition, 18 and co-sputtering 19 ) and solution-based (i.e., chemical bath deposition, 6,20 electrodeposition, 7 spray pyrolysis, 21 spin coating, 3 solvo/hydrothermal, 22,23 and hot injection 2,4,24 ) synthetic methods have been employed in the successful synthesis of CuSbS 2 thin films and nanomaterials.…”

Two-dimensional copper based colloidal nanocrystals: synthesis and applications

“…6d and e). 55 However, changing the S-source to thioacetamide produced nanocomposites of Cu 3 SbS 4 particles on CuSbS 2 nanoplates (Fig. 6d and e).…”

“…54 Introduction of transition metals, group IV and group V elements into Cu-chalcogenide 2D NCs resulted in the following compositions of CuSbS 2 , Cu 3 SbS 3 , Cu 3 BiS 3 , Cu 2 SnS 3 , Cu 2 SnSe 3 , Cu 2 GeS 3 , CuFeS 2 , Cu 2 SnZnSe 4 , Cu 2 GeZnSe 4 , etc . 22,37,55–61 More recently, metal halides of Cu with compositions of Cs 3 Cu 2 I 5 , Cs 3 Cu 2 Br 5 and Rb 2 CuX 3 (X = Cl, Br) have also been synthesised. 35,62 Among the metallic Cu 2D NCs seeded growth materialised NCs with PdCu and PdPtCu compositions.…”

“…Among the other semiconductor NCs are multinary CuInS 2 nanodiscs, nanosheets, CuSbS 2 nanosheets, and Cu 3 BiS 3 nanoplatelets using heat-up and hot-injection approaches. 21,52,55,56,70 Initial approaches for synthesising CuInS 2 were based on the heat-up of the metal precursor and S source. But extension of the elemental composition to quaternary by the introduction of Ga and Se required a more controlled hot-injection approach where cation and anion introduction windows can be separated based on the injection temperature.…”

“…For group V based NCs, heat up techniques are based on the decomposition of diethyldithiocarbamate precursors of metals. 55,56 Using the cation exchange of Cu 2− x S and Cu 2− x Se 2D templates several heterostructures and multinary nanoplates with more complex compositions involving Au, Ag, Cd, Zn, Hg, Pb, Pd, In, Ga, Fe, Sn, and Ge have also been achieved in recent times. 61 The recent addition to the ion exchange series is the anion exchange of the Cu 3− x P template for the materialisation of Cu 3 P 1− x S x nanorings.…”