Atomic Layer Deposition of Multi-Component Films Using Precursor Co-Dosing

Abstract

A growing number of ALD applications require the deposition of ternary or quarternary compounds. Examples include doped films (e.g. ZnO:Al), mixed oxides to tune dielectric properties (e.g. HfZrO), tunable bandgap materials for solar cells (e.g. ZnOS) or opto-electronic materials (e.g. InGaN), and high mobility oxide semiconductors (e.g. InGaZnO). A common method to deposit multicomponent films in ALD is the supercycle approach [1], where sub-cycles of different binary compounds are combined to deposit films where the resulting net composition is determined by the cycle ratio of the individual sub-cycles. A drawback of the supercycle method is that essentially multilayer stacks are deposited instead of true alloys and the film composition varies out-of-plane, potentially impacting film properties.An alternative method is to use precursor co-dosing, where two or more precursors are simultaneously dosed and co-adsorb during a half-reaction. The resulting film composition is then determined by the ratio of the partial pressures of the individual precursors during the precursor dose. As each ALD cycle deposits a true alloy, it results in excellent out-of-plane compositional uniformity. The co-dosing method has first been reported in the late 1980’s to deposit ternary and quarternary III-V compounds [2] and has been used since for a wide range of materials. In the last decade it has become the method of choice for depositing multicomponent materials with Spatial ALD.A proper understanding of the relation between film composition and precursor partial pressure during co-dosing is essential for accurate control of the film composition. This is not straightforward, as the surface chemistry of co-dosing can be quite complex, involving competitive adsorption, heterogeneity of reactive sites, exchange reactions and more. We will discuss how the surface chemistry of precursor co-dosing determines the film composition. In analogy to the IUPAC classification of adsorption isotherms for single adsorbents [3], we will introduce a similar classification of adsorption isotherms for multiple absorbing precursors which we will use to review and explain results reported in literature. Finally, we will discuss some interesting new opportunities for co-dosing, such as the deposition of gradient composition films and the use of co-dosing for area-selective deposition.[1]: A. Mackus et al, Chem. Mater. 31 (2019) 1142[2]: M. Tischler, S. Bedair, J. Cryst. Growth 77 (1986) 89[3]: M. Thommes et al, Pure & Appl. Chem. 87 (2015) 87