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Germanium combined with high-κ dielectrics has recently been put forth by the semiconductor industry as potential replacement for planar silicon transistors, which are unlikely to accommodate the severe scaling requirements for sub-45-nm generations. Therefore, we have studied the atomic layer deposition (ALD) of HfO2 high-κ dielectric layers on HF-cleaned Ge substrates. In this contribution, we describe the HfO2 growth characteristics, HfO2 bulk properties, and Ge interface. Substrate-enhanced HfO2 growth occurs: the growth per cycle is larger in the first reaction cycles than the steady growth per cycle of 0.04 nm. The enhanced growth goes together with island growth, indicating that more than a monolayer coverage of HfO2 is required for a closed film. A closed HfO2 layer is achieved after depositing 4–5 HfO2 monolayers, corresponding to about 25 ALD reaction cycles. Cross-sectional transmission electron microscopy images show that HfO2 layers thinner than 3 nm are amorphous as deposited, while local epitaxial crystallization has occurred in thicker HfO2 films. Other HfO2 bulk properties are similar for Ge and Si substrates. According to this physical characterization study, HfO2 can be used in Ge-based devices as a gate oxide with physical thickness scaled down to 1.6 nm. [ABSTRACT FROM AUTHOR]

Atomic layer deposition (ALD) is used in applications where inorganic material layers with uniform thickness down to the nanometer range are required. For such thicknesses, the growth mode, defining how the material is arranged on the surface during the growth, is of critical importance. In this work, the growth mode of the zirconium tetrachloride/water and the trimethyl aluminum/water ALD process on hydrogen-terminated silicon was investigated by combining information on the total amount of material deposited with information on the surface fraction of the material. The total amount of material deposited was measured by Rutherford backscattering, x-ray fluorescence, and inductively coupled plasma–optical emission spectroscopy, and the surface fractions by low-energy ion scattering. Growth mode modeling was made assuming two-dimensional growth or random deposition (RD), with a “shower model” of RD recently developed for ALD. Experimental surface fractions of the ALD-grown zirconium oxide and aluminum oxide films were lower than the surface fractions calculated assuming RD, suggesting the occurrence of island growth. Island growth was confirmed with transmission electron microscopy (TEM) measurements, from which the island size and number of islands per unit surface area could also be estimated. The conclusion of island growth for the aluminum oxide deposition on hydrogen-terminated silicon contradicts earlier observations. In this work, physical aluminum oxide islands were observed in TEM after 15 ALD reaction cycles. Earlier, thicker aluminum oxide layers have been analyzed, where islands have not been observed because they have already coalesced to form a continuous film. The unreactivity of hydrogen-terminated silicon surface towards the ALD reactants, except for reactive defect areas, is proposed as the origin of island growth. Consequently, island growth can be regarded as “undesired surface-selective ALD.” [ABSTRACT FROM AUTHOR]

Low energy ion scattering is used to selectively probe the outermost atomic layer of the surface. The development of double toroidal analyzers has improved the detection sensitivity of low energy ion scattering by orders of magnitude. The features of these analyzers are discussed. It is shown that the absence of matrix effects makes it possible to quantify the surface density of fluorine in polymers with a LiF(1 0 0) surface. The extreme surface sensitivity of LEIS also enables one to study intramolecular segregation processes. As an example the aging of a polypropylene surface that has been activated with atomic oxygen is described. As an example of the LEIS analysis of highly dispersed isolating surfaces, the formation of coke on a commercial three-way catalyst is discussed. [Copyright &y& Elsevier]