In the relentless pursuit of advancing semiconductor technology, interconnect metallization stands as a cornerstone for achieving superior electrical performance in integrated circuits. Copper (Cu) has long been the stalwart metal of choice, predominantly utilized through the Damascene plating technique, owing to its exceptional conductivity and integration feasibility. However, as the industry pushes into the realms of 14-nanometer nodes and beyond, the physical phenomena dictating electron transport begin to challenge the dominance of copper. At these minuscule scales, electron scattering at surfaces and grain boundaries severely elevates the resistivity of copper interconnects, especially in the narrow bottom-layer lines where dimensions become critically limiting.
This escalation in resistance is intrinsically linked to the interplay between the bulk resistivity (ρ_b) of the metal and the electron mean free path (λ). Together, their product, ρ_b × λ, serves as a fundamental metric governing the overall resistivity behavior in nanoscale metallic interconnects. In this context, alternative metals such as cobalt (Co), ruthenium (Ru), rhodium (Rh), and molybdenum (Mo) have emerged as promising candidates. These metals inherently possess lower ρ_b × λ values compared to copper, suggesting a natural advantage in maintaining lower resistances within confined nanoscale geometries. Furthermore, their superior melting points confer added resilience against electromigration phenomena, a significant reliability concern in operational microchips.
Among these contenders, cobalt has attracted considerable attention for its viability in commercial electroplating applications. The relative abundance and cost-effectiveness of cobalt, combined with a simpler plating process, position it favorably within the industry roadmap. Nevertheless, the transition from copper to cobalt interconnects necessitates a profound understanding of the interface chemistry, particularly relating to the organic additives pivotal for efficient cobalt electroplating via superfilling. Superfilling—also known as bottom-up filling—is a critical process that enables void-free and seamless metal deposition into high aspect ratio features like vias and trenches, an essential attribute for ensuring robust electrical pathways.
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Recent investigations have turned the spotlight on the interfacial behavior of model organic additives, notably sodium 2-mercapto-5-benzimidazolesulfonate (MBIS), a molecule validated in scientific literature for its effectiveness in cobalt superfilling. To dissect the molecular-scale interactions at the electrode-electrolyte boundary, researchers have leveraged state-of-the-art experimental techniques, including in situ surface-enhanced infrared absorption spectroscopy (SEIRAS) and electrochemical quartz crystal microbalance (EQCM) measurements. These methodologies provide unprecedented real-time insights into adsorption dynamics and mass changes during cobalt electrodeposition, supplemented by sophisticated density functional theory (DFT) calculations and molecular dynamics (MD) simulations to elucidate the underlying atomic-level mechanisms.
The findings reveal that MBIS adsorbs nearly perpendicularly onto cobalt surfaces through thiolate bonds, a configuration that significantly hampers the reduction current associated with the electrochemical processes. This adsorption effectively blocks active cobalt sites on the electrode, altering the deposition kinetics. Intriguingly, this modification results in a counterintuitive shift in faradaic efficiencies, where the hydrogen evolution reaction (HER) experiences an increase while cobalt deposition efficiency decreases. Contributing factors include the formation of cobalt(II)-MBIS complexes and an augmented interfacial concentration of free water molecules, both of which interplay to modulate the electrochemical environment intricately.
Moreover, the coverage and activity of MBIS on the cobalt electrode surface exhibit dynamic sensitivity to changes in pH and applied electrode potential. Such responsiveness likely underpins the spatially dependent behavior of cobalt superfilling observed in practical semiconductor manufacturing scenarios, particularly within the variable environments of interconnect vias. This nuanced understanding of additive functionality clarifies long-standing ambiguities regarding cobalt electroplating uniformity and provides a predictive framework to tailor additives for optimal filling performance.
Beyond empirical characterization, the research pioneers the first direct infrared spectroscopic evidence of additive adsorption on cobalt electrodes, marking a significant advancement in interface chemistry knowledge. This breakthrough sets the stage for constructing validated simulation models that marry adsorption kinetics with electrochemical superfilling dynamics. Such models are invaluable for predicting plating behavior, optimizing electrolyte formulations, and ultimately facilitating the adoption of cobalt interconnects in next-generation chip architectures.
The implications of this work are multidimensional. Technologically, it paves the way for overcoming scalability bottlenecks imposed by copper-based metallization, addressing both electrical and thermal reliability challenges. Scientifically, it enriches the fundamental comprehension of metal-electrolyte interfacial phenomena, particularly concerning complex organic additive interactions. From an industrial perspective, insights garnered here streamline the path toward sustainable and cost-effective cobalt-based fabrication processes, thereby aligning with the economic and environmental imperatives of semiconductor manufacturing.
As the semiconductor industry continues its inexorable march toward atomic-scale device features, the evolution of interconnect materials and processes becomes non-negotiable. This research not only identifies cobalt as a formidable contender but also establishes a robust methodological template for interrogating and engineering electrochemical interfaces. By integrating high-resolution spectroscopic tools with rigorous theoretical frameworks, the study exemplifies how interdisciplinary approaches can unravel the complexities that underpin future material innovations.
In conclusion, this pioneering investigation into the interfacial electrochemistry of MBIS additives at cobalt electrodes offers critical insights that could redefine metal electroplating strategies for nanoscale interconnects. The ability to modulate additive adsorption dynamically and understand its effects on deposition kinetics and selectivity illuminates pathways toward achieving defect-free, high-performance metallic features essential for sustaining Moore’s Law and beyond. As cobalt interconnect technology moves closer to industrial realization, the fundamental principles elucidated here will undoubtedly serve as a cornerstone in guiding next-generation chip manufacturing paradigms.
Subject of Research: Interfacial electrochemistry and organic additive functionality in cobalt electrodeposition for nanoscale semiconductor interconnects.
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Web References:
http://dx.doi.org/10.1007/s11426-025-2626-2
Keywords: Physical sciences; Chemistry
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