Change of the oxidation state of phosphorus in sputtered Li3±xPO4±y and Li3±xPO4±yNz films

Thin Li_3±xPO_4±yN_zLi⁺- electrolyte films prepared by reactive rf-magnetron sputtering of Li₃PO₄ incorporate a certain amount of nitrogen which is made responsible for increased Li⁺-conductivity as well as at least kinetic stability with lithium metal. A possible change of the oxidation state +5 of phosphorus as a result of the sputter process has not yet been considered for explanation. We have found out that it cannot be generally assumed that reactive low power rf-magnetron sputtering of Li₃PO₄ results in fully oxidized films, even when pure O₂ is employed as sputtering gas. Our films immediately react with H₂O releasing a garlic smelling gas. The reaction area is surrounded by a white crust afterwards. CuSO₄ and AgNO₃ aqueous solutions become reduced. Impedance measurements yield an ionic conductivity of 2·10⁻⁶ S/cm at 25 °C and an activation energy of 0.62 eV.