Atomic layer deposited tungsten nitride thin films as a new lithium-ion battery anode.

This article demonstrates the atomic layer deposition (ALD) of tungsten nitride using tungsten hexacarbonyl [W(CO)6] and ammonia [NH3] and its use as a lithium-ion battery anode. In situ quartz crystal microbalance (QCM), ellipsometry and X-ray reflectivity (XRR) measurements are carried out to confirm the self-limiting behaviour of the deposition. A saturated growth rate of ca. 0.35 Å per ALD cycle is found within a narrow temperature window of 180-195 °C. In situ Fourier transform infrared (FTIR) vibrational spectroscopy is used to determine the reaction pathways of the surface bound species after each ALD half cycle. The elemental presence and chemical composition is determined by XPS. The as-deposited material is found to be amorphous and crystallized to h-W2N upon annealing at an elevated temperature under an ammonia atmosphere. The as-deposited materials are found to be n-type, conducting with an average carrier concentration of ca. 10(20) at room temperature. Electrochemical studies of the as-deposited films open up the possibility of this material to be used as an anode material in Li-ion batteries. The incorporation of MWCNTs as a scaffold layer further enhances the electrochemical storage capacity of the ALD grown tungsten nitride (WNx). Ex situ XRD analysis confirms the conversion based reaction mechanism of the as-grown material with Li under operation.

Atomic layer deposited molybdenum nitride thin film: a promising anode material for Li ion batteries.

Molybdenum nitride (MoNx) thin films are deposited by atomic layer deposition (ALD) using molybdenum hexacarbonyl [Mo(CO)6] and ammonia [NH3] at varied temperatures. A relatively narrow ALD temperature window is observed. In situ quartz crystal microbalance (QCM) measurements reveal the self-limiting growth nature of the deposition that is further verified with ex situ spectroscopic ellipsometry and X-ray reflectivity (XRR) measurements. A saturated growth rate of 2 Å/cycle at 170 °C is obtained. The deposition chemistry is studied by the in situ Fourier transform infrared spectroscopy (FTIR) that investigates the surface bound reactions during each half cycle. As deposited films are amorphous as observed from X-ray diffraction (XRD) and transmission electron microscopy electron diffraction (TEM ED) studies, which get converted to hexagonal-MoN upon annealing at 400 °C under NH3 atmosphere. As grown thin films are found to have notable potential as a carbon and binder free anode material in a Li ion battery. Under half-cell configuration, a stable discharge capacity of 700 mAh g(-1) was achieved after 100 charge-discharge cycles, at a current density of 100 µA cm(-2).