Formation of highly conformal spinel lithium titanate thin films based on a novel three-step atomic layer deposition process

Lithium titanate (Li₄Ti₅O₁₂) (LTO) has several promising properties with regard to energy storage. The most important is its low volume expansion during lithium (de-) intercalation enabling the material for complex three-dimensional battery anode designs. To employ this property at a small scale, e.g., for micro batteries (<100 nm active layer thickness), a highly conformal deposition process like atomic layer deposition (ALD) is needed. However, the ALD of lithium containing layers is quite ambitious. Particularly, thermally activated deposition of lithium containing layers with water as a coreactant is challenging due to the high reactivity and hygroscopic nature of many lithium compounds, e.g., lithium hydroxide. That is why a novel ALD process regime has been developed, which allows the deposition of highly conformal and single phase LTO layers with excellent step coverage and composition. The process uses two metalorganic precursors: one acting as lithium and another as a titanium source. In contrast to usual ALD processes, these two precursors are subsequently applied. The reactive pulse with water is applied after the two metal precursor pulses. In this work, this novel ALD process sequence has been introduced and successfully demonstrated on 200 mm wafers using standard industrial ALD equipment. The layers are transformed to single phase Li₄Ti₅O₁₂ by rapid thermal processing as proven by crystal phase analysis. Elemental composition has been analyzed by time of flight secondary ion mass spectrometry and x-ray photoelectron spectroscopy (XPS). Results show that the amounts of contaminants like carbon and chlorine are below the detection limits of XPS. Also, a uniform element distribution and stoichiometry in good agreement with theoretical expectations for lithium titanate could be shown.