Deposition of MnO Anode and MnO <sub>2</sub> Cathode Thin Films by Plasma Enhanced Atomic Layer Deposition Using the Mn(thd) <sub>3</sub> Precursor

Publication Type:

Journal Article

Source:

Chemistry of Materials, Volume 27, Issue 10, p.3628 - 3635 (2015)

URL:

http://pubs.acs.org/doi/abs/10.1021/acs.chemmater.5b00255http://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.5b00255

Abstract:

Atomic layer deposition (ALD) of a wide range of Mn oxides (MnO to MnO2) is demonstrated by combining the Mn(thd)3 (tris(2,2,6,6-tetramethyl-3,5-heptanedionato)- manganese) precursor with different types of plasma activated
reactant gases. Typical ALD behavior is found with hydrogen, ammonia, and water plasma, with a fully precursor controlled temperature window (from 140 to 250 °C) and constant growth rate (0.022 ± 0.001 nm/cycle). A purely ligandexchange
chemistry would predict Mn2O3 films with the transition metal in the +III state. However, it is found that the nature of the processgas or -plasma, more specific its oxidizing/reducing character, largely determines the oxidation state of the grown films. Our approach provides an effective method for the deposition of MnO2(+IV), Mn3O4(+II/+III), and MnO(+II) based on the Mn(thd)3(+III) precursor. All as-deposited films are found to be smooth (<1.2 nm rms roughness), crystalline and with <6% impurities. The resulting films are tested as lithium-ion battery electrodes, showing the MnO2 and the MnO films as possible candidate thin-film cathode and anode, respectively.

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