The short-ranged bonding structure of organosilicate glasses can vary to a great extent and is directly linked to the mechanical properties of the thin film material. The combined action of ultraviolet (UV) radiation and thermal activation is shown to generate a pronounced rearrangement in the bonding structure of thin organosilicate glass films involving no significant compositional change or film densification. Nuclear magnetic resonance spectroscopy indicates loss of –OH groups and an increase of the degree of cross-linking of the organosilicate matrix for UV-treated films. Fourier transform infrared spectroscopy shows a pronounced enhancement of the Si–O–Si network bond structure, indicating the formation of more energetically stable silica bonds. Investigation with x-ray reflectivity and ellipsometric porosimetry indicated only minor film densification. As a consequence, the mechanical properties of microporous organosilicate dielectric films are substantially enhanced while preserving the organosilicate nature and pristine porosity of the films. UV-treated films show an increase in elastic modulus and hardness of more than 40%, and a similar improvement in fracture energy compared to untreated films. A minor increase in material dielectric constant from 3.0 to 3.15 was observed after UV treatment. This mechanism is of high relevance for the application of organosilicate glasses as dielectric materials for microelectronics interconnects, for which a high mechanical stability and a low dielectric constant are both essential film requirements.
A 3‐aminopropyltrimethoxysilane‐derived self‐assembled monolayer (NH2SAM) is investigated as a barrier against copper diffusion for application in back‐end‐of‐line (BEOL) technology. The essential characteristics studied include thermal stability to BEOL processing, inhibition of copper diffusion, and adhesion to both the underlying SiO2 dielectric substrate and the Cu over‐layer. Time‐of‐flight secondary ion mass spectrometry and X‐ray spectroscopy (XPS) analysis reveal that the copper over‐layer closes at 1–2‐nm thickness, comparable with the 1.3‐nm closure of state‐of‐the‐art Ta/TaN Cu diffusion barriers. That the NH2SAM remains intact upon Cu deposition and subsequent annealing is unambiguously revealed by energy‐filtered transmission electron microscopy supported by XPS. The SAM forms a well‐defined carbon‐rich interface with the Cu over‐layer and electron energy loss spectroscopy shows no evidence of Cu penetration into the SAM. Interestingly, the adhesion of the Cu/NH2SAM/SiO2 system increases with annealing temperature up to 7.2 J m−2 at 400 °C, comparable to Ta/TaN (7.5 J m−2 at room temperature). The corresponding fracture analysis shows that when failure does occur it is located at the Cu/SAM interface. Overall, these results demonstrate that NH2SAM is a suitable candidate for subnanometer‐scale diffusion barrier application in a selective coating for copper advanced interconnects.
As scaling becomes increasingly difficult, 3D integration has emerged as a viable alternative to achieve the requisite bandwidth and power efficiency challenges. However mechanical stress induced by the through silicon vias (TSV) is one of the key constraints in the 3D flow that must be controlled in order to preserve the integrity of front end devices. For the first time an extended and comprehensive study is given for the stress induced by single-and arrayed TSVs and its impact on both analog and digital FEOL devices and circuits. This work provides a complete experimental assessment and quantifies the stress distribution and its effect on front end devices. By using a combined experimental and theoretical approach we provide a framework that will enable stress aware design and the right definition of keep out zone and ultimately save valuable silicon area.
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