All solid-state ion layers has an ever-growing interest in order to accomplish on-chip energy storage devices. As such, lithium-ion synaptic transistor to build artificial neural networks, integrated area-enhanced capacitors and lithium-ion microbatteries for energy supply are suitable candidates fulfilling energy-efficient devices. Atomic layer deposition (ALD) is one of the most promising techniques for manufacturing ultrathin layers for lithium-ion devices with exceptional capabilities to enable conformal growth at atomic scale. In this area, in situ diagnostics has become of vital importance for the growth process understanding especially on view of the air-sensitivity character of lithium ultra-thin layers.The purpose of this work is to present an in situ spectroscopic ellipsometry (SE) study of ALD thin films used on the fabrication of lithium-ion devices. We will consider several aspects of ALD ultrathin films growth, such as film thickness, saturation curves and initial films nucleation. We shall compare in situ SE results with those of ex situ diagnostics such as XRR (x-ray reflectometry) and XPS (x-ray photoelectron spectroscopy).We focus on the characterization of 10-100 nm thin lithium phosphate electrolyte with and without nitrogen doping deposited at ALD temperature range 300-350°C using LiHMDS-TMPO and LiHMDS-DEPA precursors, respectively. On the other hand, the realization of silicon integrated lithium ionic devices requires the implementation of essential barrier films to prevent Li-ion into the Si substrate. We will explore here the ability of titanium nitride depositions to act as lithium-ion diffusion barriers. TiN deposition (10-20 nm thin) by ALD process (350°C-400°C) uses TiCl4 and NH3 precursors.First, we investigate the growth process of LiPO, LiPON and TiN intrinsic layers deposited using thermal ALD. Secondly, we apply in situ and ex situ diagnostics on exemplary LiPO/LiPON deposited on top of the 10 nm ALD TiN film (Figure 1: Monitoring of LiPON thickness vs deposition time using in-situ Ellipsometry). The film thickness deduced from in situ SE measurements was corroborated by thickness measurements with XRR technique (Figure 2: Evolution of LiPON thickness vs ALD cycles using Ellipsometry and SE characterization techniques). Ex situ SE was used most often for WiW uniformity evaluating (Figure 3: 8” Wafer thickness mapping of ALD LiPON layers (a: 10nm TiN film; b: 17nm LiPON film). The preliminary results underline the fact that ALD growth rate and nucleation of lithium electrolyte and titanium nitride obviously depends on the ALD process parameters (temperature, pulse and purge times, number of cycles) but on the substrate nature (silicon, thermal oxide, and metallic). In situ and ex situ diagnostics highlight that initial film growth of lithium electrolytes and TiN layers strongly depends on the precursors kind used in the ALD process and the substrate material employed. Figure 1