Thin films of hafnium oxide (HfO 2 ), gadolinium oxide (Gd 2 O 3 ), and praseodymium oxide (PrO x ) have been deposited by liquid injection atomic layer deposition (ALD) and for comparison, have also been deposited by ªthermalº metal-organic (MO) CVD using the same reactor. The ALD-grown films were deposited on Si(100) over a range of substrate temperatures (150±450 C) using alternate pulses of [Hf(mmp) 4 ], [Gd(mmp) 3 ], or [Pr(mmp) 3 ] (mmp = OCMe 2 CH 2 OMe) and water vapor. X-ray diffraction (XRD) analysis showed that as-grown films of HfO 2 were amorphous, but these crystallized into the monoclinic phase after annealing in air at 800 C. XRD analysis showed that as-grown Gd 2 O 3 and PrO x films had some degree of crystallinity. Residual carbon (0.8±3.3 at.-%) was detected in the HfO 2 and PrO x films by Auger electron spectroscopy (AES), but not in the Gd 2 O 3 films. The self-limiting behavior of the precursors was investigated at 225 C by varying the volume of precursor injected during each ALD cycle and, in each case, oxide growth was not fully self-limiting. We propose a mechanism for this involving b-hydride elimination of the mmp group, and also propose some general mechanistic principles which may influence the growth of oxides by ALD using other precursors.

A number of high-permittivity (j) dielectric oxides are currently being investigated as alternatives to SiO 2 as the dielectric insulating layer in sub-0.1 lm CMOS technology. Metal-organic (MO)CVD and atomic layer deposition (ALD) are promising techniques for the deposition of these high-j dielectric oxides. In this paper it is shown how the use of "designed" metal alkoxide precursors, containing bidentate donor-functionalized alkoxide ligands, in MOCVD leads to a marked improvement in the physical properties of the MOCVD precursors and process parameters. However, the use of such ligands is not as beneficial in the ALD process, highlighting the very different requirements of MOCVD and ALD precursors.

x , have been deposited by liquid injection MOCVD using the volatile gadolinium alkoxide precursor, [Gd(mmp) 3 ] (mmp = 1-methoxy-2-methyl-2-propanolate, OCMe 2 CH 2 OMe). Carbon-free GdO x films were grown over a wide range of substrate temperatures (300±600 C) on both Si(100) and GaAs(100) substrates. X-ray diffraction (XRD) data indicated that GdO x films grown on Si(100) were amorphous at low deposition temperatures, and crystalline with a C-type structure at growth temperatures of 450 C and above. GdO x films grown on GaAs at 450 C showed a strong preferred orientation, dominated by the (222) reflection.

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