ABSTRACT
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.
ABSTRACT
The electrochemical behavior of indium in the ionic liquid trihexyl(tetradecyl)phosphonium chloride (Cyphos IL 101) was studied. Cyphos IL 101 first had to be purified, as the impurities present in commercial Cyphos IL 101 interfered with the electrochemical measurements. Electrochemical deposition of indium metal from this electrolyte occurs without hydrogen evolution, increasing the cathodic current efficiency compared to deposition from water and avoiding porosity within the deposited metal. Indium(iii) is the most stable oxidation state in the ionic liquid. This ion is reduced in two steps, first from indium(iii) to indium(i) and subsequently to indium(0). The high thermal stability of Cyphos IL 101 allowed the electrodeposition of indium at 120 °C and 180 °C. At 180 °C indium was deposited as liquid indium which allows for the easy separation of the indium and the possibility to design a continuous electrowinning process. On molybdenum, indium deposits as liquid droplets even below the melting point of indium. This was explained by the combination of melting point depression and undercooling. The possibility to separate indium from iron and zinc by electrodeposition was tested. It is possible to separate indium from zinc by electrodeposition, but iron deposits together with indium.
ABSTRACT
Manganese(ii)-containing ionic liquids were synthesized, in which the manganese atoms are coordinated by glymes (diglyme, triglyme, tetraglyme), pyridine-N-oxide, dimethylsulfoxide or N-alkylimidazoles (N-methylimidazole, N-butylimidazole and N-hexylimidazole). As anion, bis(trifluoromethanesulfonyl)imide (bistriflimide, Tf2N-), trifluoromethanesulfonate (triflate, OTf-) or methanesulfonate (mesylate, OMs-) were used. The compounds were characterized by CHN analysis, FTIR, DSC and single-crystal X-ray diffraction measurements. All manganese atoms were six-coordinate. It was found that the glyme-type ligands were replaced by atmospheric water upon leaving the crystals open to the air for several days. The crystal structures of seven compounds were described in detail and the compounds with the lowest melting temperatures were tested as electrolytes for the electrodeposition of manganese (thin) films. An irreversible reduction wave from Mn(ii) to Mn(0) and granular manganese deposits were observed for all compounds, except for liquid manganese salts with N-alkylimidazole ligands and bistriflimide anions, where the electrochemical formation of manganese nanoparticles was observed instead of the deposition of a manganese layer. However, for compounds with the same cation but with a triflate or methanesulfonate anion, manganese metal deposits were obtained, indicating that the nature of the anion has an important effect on the electrochemical properties of liquid metal salts.
ABSTRACT
Cobalt(ii)-containing liquid metal salts (LMS) with N-alkylimidazole ligands and bis(trifluoromethanesulfonyl)imide (bistriflimide, Tf2N-) or methanesulfonate (mesylate, OMs-) anions were synthesized and characterized. The chain length of the alkyl side chain on the imidazole ligand was varied. All compounds were characterized using CHN analysis, DSC and FTIR measurements. Single-crystal X-ray diffraction measurements were performed on six of the compounds for which single crystals of good quality could be obtained. All cobalt(ii) centers are six-coordinate with the N-alkylimidazole ligands in an octahedral configuration and the anions are non-coordinating. The same coordination environment was observed by EXAFS measurements on cobalt(ii) liquid metal salts in the liquid state. The electrochemical properties of the compounds with the lowest melting temperatures were investigated using cyclic voltammetry. It was found that part of the current was consumed in the electrodeposition of cobalt, whereas the other part of the current was consumed in the electrochemical formation of cobalt(0) nanoparticles.
ABSTRACT
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.
ABSTRACT
Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu2ZnSnS4) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source.