title: Electrochemical reduction of O2 in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ionic liquid containing Zn2+ cations: deposition of non-polar oriented ZnO nanocrystalline films.
abstract: The influence of the Zn(2+) concentration and temperature on the electrochemical reduction of O(2) in a solution of zinc bis(trifluoromethanesulfonyl)imide (Zn(TFSI)(2)) salt in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR(14)TFSI) ionic liquid is presented. ZnO nanocrystalline films were then electrodeposited, under enhanced O(2) reduction, at temperatures in the 75-150 °C range. Their morphology, chemical composition, structural and optical properties were analyzed. In contrast to the polar-oriented ZnO usually obtained from aqueous and conventional solvent based electrolytes, nanocrystalline films oriented along non-polar directions, (11 ̅10) and (11 ̅20), were obtained from this ionic liquid electrolyte. A significant content of carbon was detected in the films, pointing to the active participation and crucial effect of pyrrolidinium cation (and/or byproducts) during the electrodeposition. The films showed semiconducting behavior with an optical gap between 3.43 and 3.53 eV as measured by optical transmittance. Their room temperature photoluminescence spectra exhibited two different bands centered at ∼3.4 and ∼2.2 eV. The intensity ratio between both bands was found to depend on the deposition temperature. This work demonstrates the great potential of ionic liquids based electrolytes for the electrodeposition of ZnO nanocrystalline thin films with innovative microstructural and optoelectronic properties.
authors.affiliation: New Materials Department, CIDETEC, Centre for Electrochemical Technologies, Parque Tecnológico de San Sebastián, Paseo Miramón 196, Donostia-San Sebastián 20009, Spain.
authors.forename: Eneko
authors.initials: E
authors.lastname: Azaceta
authors.forename: Rebeca
authors.initials: R
authors.lastname: Marcilla
authors.forename: David
authors.initials: D
authors.lastname: Mecerreyes
authors.forename: Mariana
authors.initials: M
authors.lastname: Ungureanu
authors.forename: Apurba
authors.initials: A
authors.lastname: Dev
authors.forename: Tobias
authors.initials: T
authors.lastname: Voss
authors.forename: Sebastian
authors.initials: S
authors.lastname: Fantini
authors.forename: Hans-Jurgen
authors.initials: HJ
authors.lastname: Grande
authors.forename: German
authors.initials: G
authors.lastname: Cabañero
authors.forename: Ramon
authors.initials: R
authors.lastname: Tena-Zaera
mesh_terms: D002412:Cations; D004563:Electrochemistry; D007093:Imidazoles / Q000737:chemistry; D052578:Ionic Liquids / Q000737:chemistry*; D008855:Microscopy, Electron, Scanning; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011759:Pyrrolidines / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared; D015032:Zinc / Q000737:chemistry*; D015034:Zinc Oxide / Q000737:chemistry*
chemical_list: C521243:1-(hydroxyethyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)imide; D002412:Cations; D007093:Imidazoles; D052578:Ionic Liquids; D011759:Pyrrolidines; C054965:N-methylpyrrolidine; D015032:Zinc; D010100:Oxygen; D015034:Zinc Oxide