Capturing the dynamics of Ti diffusion across Ti$_x$W$_{1-x}$/Cu heterostructures using X-ray photoelectron spectroscopy

TL;DR

This study uses real-time X-ray photoelectron spectroscopy to investigate how titanium diffuses through TiW/Cu heterostructures during annealing, revealing the impact of composition on diffusion behavior and barrier effectiveness.

Contribution

It demonstrates in-situ monitoring of Ti and W diffusion in TiW/Cu stacks, providing new insights into diffusion mechanisms and barrier performance during device operation.

Findings

Ti diffuses out of the barrier and accumulates at Cu surface during annealing.

Higher Ti concentration increases Ti accumulation at the Cu surface.

W also diffuses at low Ti concentrations, indicating complex diffusion dynamics.

Abstract

Interdiffusion phenomena between adjacent materials are highly prevalent in semiconductor device architectures and can present a major reliability challenge for the industry. To fully capture and better understand these phenomena, experimental approaches must go beyond static and post-mortem studies to include in-situ and in-operando setups. Here, soft and hard X-ray photoelectron spectroscopy (SXPS and HAXPES) is used to monitor diffusion in real-time across a proxy device. The device consists of a Si/SiO\textsubscript{2}/Ti$_x$W$_{1-x}$(300 nm)/Cu(25 nm) thin film material stack, with the Ti$_x$W$_{1-x}$ film acting as a diffusion barrier between Si and Cu. The monitoring of diffusion is achieved through the continuous collection of spectra whilst in-situ annealing to 673 K. Ti within the TiW is found to be highly mobile during annealing, diffusing out of the barrier and accumulating at the Cu surface. Increasing the Ti concentration within the Ti$_x$W$_{1-x}$ film increases the quantity of accumulated Ti, and Ti is first detected at the Cu surface at temperatures as low as 550 K. Surprisingly, at low Ti concentrations ($x$ = 0.054), W is also mobile and diffuses alongside Ti. These results provide crucial evidence for the importance of diffusion barrier composition on their efficacy during device application, delivering insights into the mechanisms underlying their effectiveness and limitations.