(Invited) Selective Metal Deposition for Advanced Metallization Schemes

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'Invited'Starting from critical dimensions below 10 nm, the continuation of CMOS scaling requires the Cu replacement as an IC interconnect material by a barrierless metal with lower resistivity and better electromigration performance than Cu, such as Co and Ru. In addition, narrow dimensions of interconnect features require implementation of bottom-up metal fill schemes to mitigate defects in metal structures. At the same time, significant technological improvements are required to mitigate the pattern overlays and litho-based edge placement errors when forming multilevel structures with a half-pitch at or below 10 nm. The transition from standard multiple litho-etch deposition schemes to bottom-up area-selective deposition (ASD) is a very promising way to enable self-alignment of multilevel structures. The approaches to achieve ASD can be classified in three categories: i) intrinsic selectivity, ii) selectivity enabled by passivation of the “non-growth area” and iii) selectivity enabled by activation of the “growth area”. Among selective deposition processes, electroless deposition (ELD) and atomic layer deposition (ALD) can be effectively used due to their chemical nature and surface sensitivity. This work explores all three categories of ASD approaches for BEOL technology application, utilizing the above listed techniques for Co and Ru deposition.Intrinsically selective metal deposition can be realized for very limited number of material combinations used in IC manufacturing. Part of this work focuses on various H-based plasma treatments, which allow forming appropriate surface functionalities enabling ASD. Among various material combinations, the focus was set on amorphous carbon (a-C) as “non-growth” surface and Si-based materials, such as SiCN, as “growth” surface. An interaction of various compounds of H-based plasma, namely: H ions and H radicals with a-C was investigated experimentally. In order to support experimental observations, molecular dynamic modeling of a-C interaction with H plasma was performed, which allowed to understand the mechanisms of a-C chemical modification by H ions and radicals. Effectivity of H plasma treatment on ALD selectivity was studied for the case of selective Ru ALD using (ethylbenzyl)(1-ethyl-1,4-cyclohexadienyl)Ru(0) (EBECHRu) precursor with O2 co-reactant. In addition, an initial study of Ru ASD integration into patterned structures of technological relevant dimensions was performed.Direct implementation of intrinsically selective processes into production is a rare case in microelectronic technology. In most of the cases, however, blocking layers can be used. This work explores self-assembled monolayers (SAMs) as blocking layers for ALD. Screening of various siloxane-SAM precursors was performed to study the impact of SAM’s functional group, length of alkyl chain and deposition conditions on surface density of SAM molecules and, specifically, passivation properties of SAM against Ru ALD. An additional study was performed in order to analyze modification of (3-trimethoxysilylpropyl)diethylenetriamine (DETA)-derived SAM under ALD conditions (250 °C and O2 co-reactant). In-situ XPS as well as molecular-dynamic modelling were employed to investigate the mechanisms of DETA modification. Lastly, a removal of DETA-derived SAM from Cu “growth area” selectively with respect to SiO2 “non-growth area” using acetic acid was investigated to mitigate defectivity.Further, surface functionalization by SAMs can also be used to form appropriate surface terminal groups for further attachment of a metal catalyst or metal seed, used in subsequent selective ELD deposition. ELD is based on redox reactions on the metal substrate; therefore, it can be used for intrinsically selective metal deposition on metal substrates or metal seeds. SAMs-enabled selectivity can be used for metal growth on a dielectric surface selectively with respect to another type of the dielectric material. In the case of ELD bottom-up growth in a trench, the metal catalyst should be selectively deposited at the trench bottom dielectric layer. In this work, the selectivity of Pd metal catalyst promoted by selective surface functionalization by SAMs was investigated. It has been shown that SAMs with amino functional groups form covalent bonds with Pd catalyst, which is commonly used as a seed for subsequent ELD of various metals including Co on the Pd seed. Since the electrical properties of interconnect material are of crucial importance, an additional study of ELD Co resistivity was performed, including in-depth analysis of Co recrystallization revealing Co grain size dependency on the film resistivity.In conclusion, area-selective metal deposition processes are an important part of future microelectronic technology. This work explores ASD of Ru and Co, as the most promising Cu replacement metals. For the deposition of these metals, surface sensitive techniques are used, namely ALD and ELD. For the cases, where intrinsic selectively of the deposition technique cannot be realized for the combination of materials used in the process flow, SAM-based passivation and SAM-based activation layers were investigated.