Precursors and chemistry for the atomic layer deposition of metallic first row transition metal films

A thin diffusion barrier was self-formed by annealing at an interface between a Cu-Mn alloy film and a SiO2 substrate. The growth of the barrier layer followed a logarithmic rate law, which represents field-enhanced growth mechanism in the early stage and self-limiting growth behavior in the late stage. The barrier layer was stable at 450 °C for 100 h and at 600 °C for 10 h. The interface diffusivity was estimated from the morphology change of the barrier layer at 600 °C and was found to be smaller than the grain-boundary diffusivity of bulk Cu.

Growth kinetics and thermal stability of a self-formed barrier layer at Cu-Mn∕SiO2 interface

The evolution of copper-based interconnects requires the realization of an ultrathin diffusion barrier layer between the Cu interconnect and insulating layers. The present work reports the use of atomically thin layer graphene as a diffusion barrier to Cu metallization. The diffusion barrier performance is investigated by varying the grain size and thickness of the graphene layer; single-layer graphene of average grain size 2 ± 1 μm (denoted small-grain SLG), single-layer graphene of average grain size 10 ± 2 μm (denoted large-grain SLG), and multi-layer graphene (MLG) of thickness 5-10 nm. The thermal stability of these barriers is investigated after annealing Cu/small-grain SLG/Si, Cu/large-grain SLG/Si, and Cu/MLG/Si stacks at different temperatures ranging from 500 to 900 °C. X-ray diffraction, transmission electron microscopy, and time-of-flight secondary ion mass spectroscopy analyses confirm that the small-grain SLG barrier is stable after annealing up to 700 °C and that the large-grain SLG and MLG barriers are stable after annealing at 900 °C for 30 min under a mixed Ar and H2 gas atmosphere. The time-dependent dielectric breakdown (TDDB) test is used to evaluate graphene as a Cu diffusion barrier under real device operating conditions, revealing that both large-grain SLG and MLG have excellent barrier performance, while small-grain SLG fails quickly. Notably, the large-grain SLG acts as a better diffusion barrier than the thicker MLG in the TDDB test, indicating that the grain boundary density of a graphene diffusion barrier is more important than its thickness. The near-zero-thickness SLG serves as a promising Cu diffusion barrier for advanced metallization.

Graphene as an atomically thin barrier to Cu diffusion into Si.

https://iopscience.iop.org/article/10.1149/2.073206jes/pdf

Cobalt Polishing with Reduced Galvanic Corrosion at Copper/Cobalt Interface Using Hydrogen Peroxide as an Oxidizer in Colloidal Silica-Based Slurries

4-nm thick multilayer structure of multi-component (AlCrRuTaTiZr)Nx as robust diffusion barrier for Cu interconnects

Advancement of semiconductor devices requires the realization of an ultrathin diffusion barrier layer between Cu interconnect and insulating layers. The present work investigated the possibility of the self-forming barrier layer in Cu–Mn alloy thin films deposited directly on SiO2. After annealing at 450 °C for 30 min, a Mn containing amorphous oxide layer of 3–4 nm in thickness was formed uniformly at the interface. Residual Mn atoms were removed to form a surface oxide layer, leading to a drastic resistivity decrease of the film. No interdiffusion was detected between Cu and SiO2 within the detection limit of x-ray energy dispersive spectroscopy.

Self-forming diffusion barrier layer in Cu–Mn alloy metallization

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Self-forming diffusion barrier layer in Cu–Mn alloy metallization