Reliability of copper low-k interconnects

Annealing of MnO@SiO2 nanospheres in a reducing gas environment resulted in the transformation of the core–shell structure into a hollow structure as a result of outward diffusion of MnO species into the thermodynamically more stable silicate phase. When the hollow silicate nanospheres were oxidized, the interior cavities were refilled with a Mn3O4 phase segregated from the silicate phase, and the hollow structure reverted to the initial core–shell structure. More interestingly, when catalytically active Pt nanocrystals were introduced into the manganese oxide/silica system, the Mn3O4 was readily reduced to the chemically reactive MnO, even at low temperature, which enabled reconversion of the solid nanospheres with a Mn3O4 core to hollow nanostructures during reductive annealing. Therefore, when MnO@SiO2/Pt(II) nanospheres were subjected to an oxidation/reduction cycle by repeatedly switching the flowing gas between air and hydrogen, the nanospheres underwent a reversible change between solid and hollow ...

Reversible and Cyclical Transformations between Solid and Hollow Nanostructures in Confined Reactions of Manganese Oxide and Silica within Nanosized Spheres

A diffusion barrier layer of a few nanometers in thickness is required for a Cu/SiO2 interconnect structure for advanced integrated circuits (ICs). This paper reports a new barrier material and process by chemical vapor deposition (CVD) of a Mn oxide layer using a bis(ethylcyclopentadienyl)manganese precursor. A good adhesion was obtained when the MnOx layer was deposited below 300°C because of the small amount of carbon inclusion within the layer. The metal-oxide-semiconductor samples of Cu/MnOx/SiO2/p-Si showed a very low leakage current of less than 10-7 A/cm2 at 4 MV/cm and a negligible shift of the flat-band voltage after thermal annealing and bias temperature annealing. The obtained results indicated that the CVD-deposited MnOx is an excellent diffusion barrier layer for advanced ICs.

Structural and Electronic Properties of a Mn Oxide Diffusion Barrier Layer Formed by Chemical Vapor Deposition

Mn/Cu heterostructures thermally evaporated onto SiO2 and, subsequently, annealed were investigated by transmission electron microscopy related techniques in order to study the diffusion interactions which lead to barrier layer formation. Energy dispersive x-ray spectroscopy and electron energy loss spectroscopy provide evidence for the interdiffusion between the Mn and Cu layers following a 450 °C anneal, where the Mn diffuses toward the surface of the structure, while Cu diffuses toward the Mn/SiO2 but does not propagate into the dielectric. The chemical composition of the 2–3 nm interfacial layer is primarily a mixture of +2 and +3 Mn valences, in good agreement with previously reported results.

Interdiffusion and barrier layer formation in thermally evaporated Mn/Cu heterostructures on SiO2 substrates

In this study, Mn silicate (MnSiO3) barrier layers were formed on thermally grown SiO2 using both metallic Mn and oxidized Mn films, in order to investigate the role of oxygen in determining the extent of the interaction between the deposited Mn and the SiO2 substrate. Using x-ray photoelectron spectroscopy, it has been shown that a metallic Mn film with an approximate thickness of 1 nm cannot be fully converted to Mn silicate following vacuum annealing to 500 °C. Transmission electron microscopy (TEM) analysis suggests the maximum MnSiO3 layer thickness obtainable using metallic Mn is ∼1.7 nm. In contrast, a ∼1 nm partially oxidized Mn film can be fully converted to Mn silicate following thermal annealing to 400 °C, forming a MnSiO3 layer with a measured thickness of 2.6 nm. TEM analysis also clearly shows that MnSiO3 growth results in a corresponding reduction in the SiO2 layer thickness. It has also been shown that a fully oxidized Mn oxide thin film can be converted to Mn silicate, in the absence of m...

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Chemical and structural investigation of the role of both Mn and Mn oxide in the formation of manganese silicate barrier layers on SiO2

X-ray absorption fine structure spectroscopy has been used to study the chemical and structural properties of self-forming diffusion barrier layers from Cu-8 at. % Mn alloy films on porous low-k and thermally grown SiO2 dielectrics. For the porous low-k/Cu(Mn) system, we provide evidence that the interface is composed of MnSiO3 and MnO with near complete Mn segregation from the alloy film; however, we find that the self-forming process does not go to full completion on thermally grown SiO2 substrates.

Phase identification of self-forming Cu–Mn based diffusion barriers on p-SiOC:H and SiO2 dielectrics using x-ray absorption fine structure

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Phase identification of self-forming Cu–Mn based diffusion barriers on p-SiOC:H and SiO2 dielectrics using x-ray absorption fine structure