Lithium Spatial Distribution and Split-Off Electronic Bands at Nanoscale V_2O_5/LiPON Interfaces

A combination of depth-resolved cathodoluminescence spectroscopy (DRCLS) and X-ray photoemission depth profiling (XPS) measured the pronounced changes in both the electronic density of states and lithium composition near the nanoscale Li_xV₂O₅/LiPON interface. DRCLS studies of electrochemically lithiated bare V₂O₅ and the sputter-deposited V₂O₅ plus LiPON overlayer electrochemically lithiated in stages both showed that in the bulk the luminescence intensity of the “split-off” hybridized bonding density of states was anticorrelated with XPS-measured Li content, decreasing as the Li content increased. However, the LiPON overlayer was found to modify the band structure of the underlying Li_xV₂O₅ (LVO) to a depth of at least 30 nm beneath the V₂O₅ interface. DRCLS spectra near the electrochemically lithiated LiPON/LVO interface showed a significant intensity of the split-off band, implying a low Li content. However, XPS depth profiling revealed a pronounced negative gradient of Li extending from a maximum Li content at the intimate LiPON boundary to its lowest content of ∼30 nm into the V₂O₅ in the same region, indicating a strong interaction between band structure and Li electrochemical potential near this heterojunction. These results provide evidence for substantial effects on the local band structure near an electrolyte/cathode interface and insights into the electrochemical interface behavior of solid-state batteries in general.