Author

Jian Liu

Date of Award

2009

Degree Type

Thesis

Degree Name

Doctor of Philosophy

Program

Physics

Supervisor

Dr.Landheer

Abstract

Hafnium silicate is one of the most promising high dielectric constant (high-ft) candidates being investigated as an alternative to replace Si0 2 as a gate dielec­ tric material in complementary metal-oxide-semiconductor transistors. In this the­ sis, Hf silicate films were grown by atomic layer deposition using the liquid pre­ cursors tetrakis(diethylamido)hafnium (TDEAH) and tris(2-methyl-2-butoxy)silanol (TMBS). The dynamic growth processes were monitored by in situ spectroscopic el- lipsometry. A self-limiting growth with a rate ~1 monolayer per cycle was observed only after several initial cycles —a behaviour that is ascribed to the chemistry of the initial Si substrate surface.

The film composition, as a function of the substrate temperature and TMBS pulse time, was characterized by x-ray photoelectron spectroscopy (XPS) and medium energy ion scattering (MEIS). It was found that the Hf concentration, i.e., the Hf/(Hf+Si) value, can only be adjusted in the range 0.22—0.30; the carbon con­ tamination in the film can be minimized by assuring that the self-limiting condition is achieved for the TMBS precursor. A possible reaction mechanism between the TDEAH and TMBS precursors is proposed.

Hf distributions in the as-grown and annealed Hf silicate films with thicknesses in the range 4—20 nm were investigated by high resolution transmission electron microscopy (HRTEM), angle resolved x-ray photoelectron spectroscopy (ARXPS) and MEIS. HRTEM images showed a layered structure for films thinner than 8 nm. ARXPS data also showed a non-uniform distribution of Hf throughout the film depth. A diffusion of SiC>2 to the film surface after a longer time anneal was observed by MEIS. All these observations provide evidence for surface-directed spinodal decom­ position in the pseudobinary (Hf0 2 )x(Si0 2 )i-x alloy system.

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