High-speed electrodeposition of copper-tin-zinc stacks from liquid metal salts for Cu2ZnSnSe4 solar cells.

Cu2ZnSnSe4-based solar cells with 5.5% power conversion efficiency were fabricated from Cu/Sn/Zn stacks electrodeposited from liquid metal salts. These electrolytes allow metal deposition rates one order of magnitude higher than those of other deposition methods.

Homoleptic and heteroleptic N-alkylimidazole zinc(ii)-containing ionic liquids for high current density electrodeposition.

New homoleptic and heteroleptic zinc(ii)-containing liquid metal salts with N-alkylimidazole (AlkIm) ligands and bis(trifluoromethylsulfonyl)imide (Tf2N(-)) anions are described. The general formulae of the complexes are [Zn(AlkIm)6][Tf2N]2 and [Zn(AlkIm)6-x(AlkIm')x][Tf2N]2. Single-crystal X-ray diffraction revealed that, in the solid state, the cations consist of octahedral zinc(ii) centres. The heteroleptic complexes contain two different N-alkylimidazole ligands. The melting points of the liquid metal salts are below or slightly above room temperature. The dependence of the melting points, viscosity and crystal structure on the alkyl chain length of the N-alkylimidazole ligand for the homoleptic complexes and on the ratio of the two N-alkylimidazole ligands AlkIm and AlkIm' for the heteroleptic compounds is discussed. The possibility of incongruent melting and the presence of a mixture of the four-coordinate zinc(ii) centre and neutral ligands is discussed. The new zinc(ii)-containing liquid metal salts have been used as non-aqueous electrolytes for electrodeposition of zinc. A highly reversible deposition-stripping behaviour was found. Zinc electroplating was possible at very high current densities of more than -200 mA cm(-2) in unstirred solutions. Compact and highly crystalline zinc deposits were obtained.

Tuning the gallium content of metal precursors for Cu(In,Ga)Se2 thin film solar cells by electrodeposition from a deep eutectic solvent.

Controlling the Ga incorporation of Cu-In-Ga metal precursors for Cu(In,Ga)Se2 (CIGS) solar cells is one of the main challenges for low cost electrodeposition processes, mainly due to the difficulty in electrodepositing metallic Ga from aqueous electrolytes. In this work we use the deep eutectic solvent (DES) Choline Chloride : Urea (ChCl : U - 1 : 2) to efficiently codeposit In-Ga on Cu and Mo electrodes. We control the Ga/(Ga+In) (Ga/III) ratio of the films via the mass fluxes. The electrochemical behavior of ChCl : U containing GaCl3 and InCl3 is studied by rotating disk electrode cyclic voltammetry (CV) on Mo and Cu electrodes. CV revealed on both Mo and Cu electrodes that the electrochemical behavior of the ChCl : U-GaCl3-InCl3 system is the superposition of the individual In and Ga electrochemistry. On a Cu electrode the morphology, crystal structure and element distribution of the deposits were a function of the Ga/III ratio. We demonstrate the precise control of Ga incorporation over a large composition range from 0.1 ≤ Ga/III ≤ 0.9 and proved that ED from DES is a straightforward, robust and efficient process. First solar cells based on Mo/Cu/In-Ga metal stacks achieved efficiencies as high as 7.9% with a Voc of 520 mV.

Controlled electrodeposition of Cu-Ga from a deep eutectic solvent for low cost fabrication of CuGaSe2 thin film solar cells.

The electrochemical deposition of Ga and Cu-Ga alloys from the deep eutectic solvent choline chloride/urea (Reline) is investigated to prepare CuGaSe(2) (CGS) semiconductors for their use in thin film solar cells. Ga electrodeposition is difficult from aqueous solution due to its low standard potential and the interfering hydrogen evolution reaction (HER). Ionic liquid electrolytes offer a better thermal stability and larger potential window and thus eliminate the interference of solvent breakdown reactions during Ga deposition. We demonstrate that metallic Ga can be electrodeposited from Reline without HER interference with high plating efficiency on Mo and Cu electrodes. A new low cost synthetic route for the preparation of CuGaSe(2) absorber thin films is presented and involves the one-step electrodeposition of Cu-Ga precursors from Reline followed by thermal annealing. Rotating disk electrode (RDE) cyclic voltammetry (CV) is used in combination with viscosity measurements to determine the diffusion coefficients of gallium and copper ions in Reline. The composition of the codeposited Cu-Ga precursor layers can be controlled to form Cu/Ga thin films with precise stoichiometry, which is important for achieving good optoelectronic properties of the final CuGaSe(2) absorbers. The morphology, the chemical composition and the crystal structure of the deposited thin films are analysed by scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX) and X-ray diffraction (XRD). Annealing of the Cu-Ga films in a selenium atmosphere allowed the formation of high quality CuGaSe(2) absorber layers. Completed CGS solar cells achieved a 4.1% total area power conversion efficiency.