Durability improvement of electrochromic WO3 thin films by deposition of an ultra-thin Al2O3 layer via atomic layer deposition

Introduction of an ultra-thin Al2O3 protective layer via atomic layer deposition (ALD) significantly enhances the durability and performance of amorphous tungsten trioxide (a-WO3) thin films for electrochromic devices. The Al2O3 layer, despite being less than 4 nm thick, effectively suppresses the dissolution of WO3 that typically occurs through hydration reactions forming WO3·H2O and tungstic acid (H2WO4). XRD and XPS analyses confirmed the presence of Al2O3 and its minimal impact on the amorphous structure of WO3 thin films. Optical transmittance measurements showed that the Al2O3-protected a-WO3 thin films maintained a higher transmittance modulation (ΔT) compared to bare a-WO3 thin films, with the ALD30 sample retaining 87.9 % of its initial transmittance modulation after 1000 cycles, in contrast to the rapid degradation observed in unprotected films. Microstructural analysis revealed significantly fewer surface cracks and reduced thickness loss in Al2O3-coated films after 100 cycles. Additionally, ICP-MS analysis indicated a much lower W concentration in the electrolyte for Al2O3-protected samples, confirming reduced dissolution. © 2024 Elsevier B.V.