Direct Detection of Free H2 Outgassing in Blisters Formed in Al2O3 Atomic Layers Deposited on Si and Methods of Its Prevention

ACS Appl Mater Interfaces. 2022 Jan 12;14(1):1472-1477. doi: 10.1021/acsami.1c20660. Epub 2021 Dec 27.

Abstract

The phenomenon of blistering, seen in atomic layer-deposited aluminum oxide layers caused by thermal treatment, represents a serious problem in the field of device fabrication. Determining its causes and controlling them have been a major task in this field. Various groups have so far confronted the challenge, with several mechanisms having been proposed, but it is still under investigation. This paper reports how we have systematically characterized and summarized the blistering phenomenon from the viewpoints of annealing temperature and Al2O3-Si interface conditions. In this study, we have succeeded in directly detecting hydrogen gas generation from the interface between Si and Al2O3 using blister-penetrating Raman spectroscopy. The results have enabled us to propose a mechanism for blister formation using a hydrogen outgassing model. Based on our model, we also propose a method of suppressing blister formation by applying surface treatment or passivation to eliminate the Si-H bonds. These discoveries and methods will provide important insights that are applicable to a wide range of applications such as electronic devices and nanostructured solar cells.

Keywords: aluminum oxide; atomic layer deposition; blistering; high-k dielectric; metal oxide semiconductor; post-deposition annealing.