Integrating bottom-up area-selective building-blocks in microelectronics has a disruptive potential because of the unique capability of engineering new structures and architectures. Atomic layer deposition (ALD) is an enabling technology, yet understanding the surfaces and their modification is crucial to leverage area-selective ALD (AS-ALD) in this field. The understanding of general selectivity mechanisms and the compatibility of plasma surface modifications with existing materials and processes, both at research and production scale, will greatly facilitate AS-ALD integration in microelectronics. The use of self-assembled monolayers to inhibit the nucleation and growth of ALD films is still scarcely compatible with nanofabrication because of defectivity and downscaling limitations. Alternatively, in this Research Article, we demonstrate a straightforward H plasma surface modification process capable of inhibiting Ru ALD nucleation on an amorphous carbon surface while still allowing instantaneous nucleation and linear growth on Si-containing materials. Furthermore, we demonstrate how AS-ALD enables previously inaccessible routes, such as bottom-up electroless metal deposition in a dual damascene etch-damage free low-k replacement scheme. Specifically, our approach offers a general strategy for scalable ultrafine 3D nanostructures without the burden of subtractive metal patterning and high cost chemical mechanical planarization processes.

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The selective deposition of materials on predefined areas on a substrate is of crucial importance for various applications, such as energy harvesting, microelectronic device fabrication, and catalysis. A representative example of area-confined deposition is the selective deposition of a metal film as the interconnect material in multilevel metallization schemes for CMOS technology. This allows the formation of multilevel structures with standard lithographical techniques while minimizing pattern misalignment and overlay and improving the uniformity of the structures across the wafer. In this work, area-selective deposition of Ru by atomic layer deposition (ALD) is investigated using alkoxy siloxane dielectric passivation layers. In this work, a comparison of several silane organic SAM precursors in terms of Ru ALD ASD performance is reported. The importance of the surface areal concentration of the passivation molecules is demonstrated. According to the in situ X-ray photoelectron spectroscopy film characterization, the ALD blocking layers derived from a (3-trimethoxysilylpropyl) diethylenetriamine (DETA) precursor have the ability to polymerize under ALD-compatible temperatures, such as 250 °C, which leads to a significant inhibition of Ru growth up to 400 ALD cycles. At the same time, the DETA layer can be selectively removed from the oxidized Cu surface by rinsing in acetic acid, which allows selective deposition of ca. 14 nm of Ru on Cu with no Ru detected on the DETA-coated surface by RBS. The approach is successfully tested on 50 nm halfpitch patterned SiO 2 /Cu lines.

Selective electroless deposition of Co directly on dielectric surfaces, promoted by amino-terminated organic films in combination with a selective Pd catalyst.