Galvanostatic Rejuvenation of Electrochromic WO 3 Thin Films: Ion Trapping and Detrapping Observed by Optical Measurements and by Time-of-Flight Secondary Ion Mass Spectrometry

• Published in: ACS applied materials & interfaces 2017-05, Vol.9 (20), p.16995-17001
• Main Authors: Baloukas, Bill, Arvizu, Miguel A, Wen, Rui-Tao, Niklasson, Gunnar A, Granqvist, Claes G, Vernhes, Richard, Klemberg-Sapieha, Jolanta E, Martinu, Ludvik
• Format: Article
• Language: English
• ISSN: 1944-8244; 1944-8252
• DOI: 10.1021/acsami.7b01260

Electrochromic (EC) smart windows are able to decrease our energy footprint while enhancing indoor comfort and convenience. However, the limited durability of these windows, as well as their cost, result in hampered market introduction. Here, we investigate thin films of the most widely studied EC material, WO . Specifically, we combine optical measurements (using spectrophotometry in conjunction with variable-angle spectroscopic ellipsometry) with time-of-flight secondary ion mass spectrometry and atomic force microscopy. Data were taken on films in their as-deposited state, after immersion in a Li-ion-conducting electrolyte, after severe degradation by harsh voltammetric cycling and after galvanostatic rejuvenation to regain the original EC performance. Unambiguous evidence was found for the trapping and detrapping of Li ions in the films, along with a thickness increase or decrease during degradation and rejuvenation, respectively. It was discovered that (i) the trapped ions exhibited a depth gradient; (ii) following the rejuvenation procedure, a small fraction of the Li ions remained trapped in the film and gave rise to a weak short-wavelength residual absorption; and (iii) the surface roughness of the film was larger in the degraded state than in its virgin and rejuvenated states. These data provide important insights into the degradation mechanisms of EC devices and into means of achieving improved durability.