Polyvinylpyrrolidone (PVP) assisted single‐step synthesis of kesterite Cu2ZnSnS4 nanoparticles by solvothermal process

Quaternary kesterite‐type Cu₂ZnSnS₄ (CZTS) nanoparticles (NPs) were successfully synthesized by a single‐step solvothermal process. Semiconductor CZTS nanoparticles were obtained from ethylene glycol (EG) and CZTS precursor after solvothermal process at 180 °C for 30 h in polyvinylpyrrolidone (PVP) medium. The synthesized CZTS NPs were further annealed at 450 °C in nitrogen atmosphere and used for further characterizations. The CZTS NPs were characterized using X‐ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), micro Raman spectroscopy, high resolution transmission electron microscopy (HRTEM) and X‐ray photoelectron spectroscopy (XPS). The optical properties of the CZTS NPs were recorded by UV–vis absorption spectroscopy. The results showed that the synthesized CZTS nanoparticles are kesterite‐type CZTS, with good crystallinity and a stoichiometric composition. Moreover, the prepared nanoparticles have a size ranging from 5–7 nm and a band gap of ～1.5 eV.

     

Cu2ZnSn(S1–xSex)4 thin film solar cells prepared by water‐based solution process

The kesterite Cu₂ZnSn(S_1–xSe_x)₄ (CZTSSe) thin film solar cell has been developed rapidly due to its excellence in structural and optical properties and its abundance in raw materials. Both vacuum‐based and solution‐based methods have been successfully employed to fabricate CZTSSe thin film solar cells. In this Letter, we report an environmentally friendly, water‐based, solution process for fabrication of high‐efficiency CZTSSe thin film solar cells. High quality CZTSSe thin film is obtained by selenization under high temperature and Se vapor. An efficiency of 6.2% is achieved on CZTSSe thin film solar cell fabricated by such water‐based solution process. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

ZnSe Etching of Zn‐Rich Cu2ZnSnSe4: An Oxidation Route for Improved Solar‐Cell Efficiency

Cu₂ZnSnSe₄ kesterite compounds are some of the most promising materials for low‐cost thin‐film photovoltaics. However, the synthesis of absorbers for high‐performing devices is still a complex issue. So far, the best devices rely on absorbers grown in a Zn‐rich and Cu‐poor environment. These off‐stoichiometric conditions favor the presence of a ZnSe secondary phase, which has been proved to be highly detrimental for device performance. Therefore, an effective method for the selective removal of this phase is important. Previous attempts to remove this phase by using acidic etching or highly toxic organic compounds have been reported but so far with moderate impact on device performance. Herein, a new oxidizing route to ensure efficient removal of ZnSe is presented based on treatment with a mixture of an oxidizing agent and a mineral acid followed by treatment in an aqueous Na₂S solution. Three different oxidizing agents were tested: H₂O₂, KMnO₄, and K₂Cr₂O₇, combined with different concentrations of H₂SO₄. With all of these agents Se^2? from the ZnSe surface phase is selectively oxidized to Se⁰, forming an elemental Se phase, which is removed with the subsequent etching in Na₂S. Using KMnO₄ in a H₂SO₄‐based medium, a large improvement on the conversion efficiency of the devices is observed, related to an improvement of all the optoelectronic parameters of the cells. Improvement of short‐circuit current density (J_sc) and series resistance is directly related to the selective etching of the ZnSe surface phase, which has a demonstrated current‐blocking effect. In addition, a significant improvement of open‐circuit voltage (V_oc), shunt resistance (R_sh), and fill factor (FF) are attributed to a passivation effect of the kesterite absorber surface resulting from the chemical processes, an effect that likely leads to a reduction of nonradiative‐recombination states density and a subsequent improvement of the p–n junction.     

Proposition of an Environment Friendly Triple Junction Solar Cell Based on Earth Abundant CBTSSe/CZTS/ACZTSe Materials

We propose a triple junction CBTSSe/CZTS/ACZTSe solar cell using earth abundant and non‐toxic CBTSSe, CZTS, and ACZTSe as the primary absorbing layers for top, middle, and bottom cells, respectively. Using rigorous optoelectronic simulation, we analyze the performance of the proposed cell and vary absorber thicknesses in order to maximize its efficiency. The maximum obtainable efficiency is calculated to be 36.04% with 2.73 V open circuit voltage, 17.88 mA cm^?2 short circuit current density, and 73.7% fill factor including Shockley–Read–Hall, surface and radiative recombination mechanisms. The maximum achievable efficiency can be obtained from an optimized device structure with 250, 300, and 1000 nm thicknesses of CBTSSe, CZTS, and ACZTSe, respectively. The design and analyses presented in this work would help in achieving highly efficient eco‐friendly inorganic solar cells.     

Multistep deposition of Cu2Si(S,Se)3 and Cu2ZnSiSe4high band gap absorber materials for thin film solar cells

Cu₂ZnSi(S,Se)₄ and Cu₂Si(S,Se)₃ are potential materials to obtain cost effective high band gap absorbers for tandem thin film solar cell devices. A method to synthesize Cu₂SiS₃, Cu₂SiSe₃and Cu₂ZnSiSe₄thin film absorbers is proposed. This method is based on a multistep process, using sequential deposition and annealing processes. X‐ray diffraction analysis performed on the final thin films have confirmed the presence of the Cu₂Si(S,Se)₃ and Cu₂ZnSiSe₄phases. Scanning electron microscopy images revealed the formation of polycrystalline layers with grains size up to 1 µm. The band gap of the ternary Cu₂SiSe₃ and Cu₂SiS₃, and quaternary Cu₂ZnSiSe₄ based thin films as determined from optical and photoluminescence measurements are found to be close to their theoretical values. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Photo‐enhanced catalytic activity of spray‐coated Cu2SnSe3 nanoparticle counter electrode for dye‐sensitised solar cells

Cu₂SnSe₃ nanoparticles are synthesised using oleylamine as both a solvent and capping agent and spray coated to form dye‐sensitised solar cell (DSSC) counter electrodes (CEs) using earth‐abundant elements. The film requires annealing at only 400 °C in nitrogen, which is a lower temperature than previous reports of both Cu₂SnSe₃and Cu₂ZnSnSe₄ films, also avoiding the use of Se gas. The composition and phase of the material is confirmed to be kesterite Cu₂SnSe₃. DSSCs using Cu₂SnSe₃ CEs give a power conversion efficiency of 4.87%, compared to 5.35% when using Pt. Electrochemical impedance spectroscopy indicates that the performance of the Cu₂SnSe₃ CE is enhanced under illumination, leading to a drop in the charge transfer resistance. This illumination‐induced enhancement of the catalytic activity provides a novel mechanism for the enhancement of CE performance in DSSCs.

     

Radio frequency magnetron sputtered epitaxial Cu2ZnSnS4 thin film on ZnS(100)

Heteroepitaxial growth of kesterite Cu₂ZnSnS₄ (CZTS) thin film on cubic ZnS(100) single crystal substrate was achieved by radio frequency magnetron sputtering from a single CZTS target. An optimal substrate temperature in the range of 470–500 °C is found suitable for this epitaxial growth. The growth of CZTS was confirmed to be along a‐axis. The sputtered CZTS thin film is homogeneous throughout the whole film. The band gap of the film is found to be approximately 1.51 eV, i.e., promising for high efficiency thin film solar cells.