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The structure of self-assembled monolayers (SAMs) of undecylenic acid methyl ester (SAM-1) and undec-10-enoic acid 2-bromo-ethyl ester (SAM-2) grown on hydrogen-passivated Si(111) were studied by X-ray reflectivity (XRR), X-ray standing waves (XSW), X-ray fluorescence (XRF), atomic force microscopy, and X-ray photoelectron spectroscopy (XPS). The two different SAMs were grown by immersion of H-Si(111) substrates into the two different concentrated esters. UV irradiation during immersion was used to create Si dangling bond sites that act as initiators of the surface free-radical addition process that leads to film growth. The XRR structural analysis reveals that the molecules of SAM-1 and SAM-2 respectively have area densities corresponding to 50% and 57% of the density of Si(111) surface dangling bonds and produce films with less than 4 angstroms root-mean-square roughness that have layer thicknesses of 12.2 and 13.2 angstroms. Considering the molecular lengths, these thicknesses correspond to a 38 degrees and 23 degrees tilt angle for the respective molecules. For SAM-2/Si(111) samples, XRF analysis reveals a 0.58 monolayer (ML) Br total coverage. Single-crystal Bragg diffraction XSW analysis reveals (unexpectedly) that 0.48 ML of these Br atoms are at a Si(111) lattice position height that is identical to the T1 site that was previously found by XSW analysis for Br adsorbed onto Si(111) from a methanol solution and from ultrahigh vacuum. From the combined XPS, XRR, XRF, and XSW evidence, it is concluded that Br abstraction by reactive surface dangling bonds competes with olefin addition to the surface.

Plastic zone evolution in Al-2 wt% Si metal films on silicon and sapphire substrates was studied using nanoindentation and atomic force microscopy (AFM). AFM was used to measure the extent of plastic pileup, which is a measure of the plastic zone radius in the film. It was found that the plastic zone size develops in a self-similar fashion with increasing indenter penetration when normalized by the contact radius, regardless of film hardness or underlying substrate properties. This behavior was used to develop a hardness model that uses the extent of the plastic zone radius to calculate a core region within the indenter contact that is subject to an elevated contact pressure. AFM measurements also indicated that as film thickness decreases, constraint imposed by the indenter and substrate traps the film thereby reducing the pileup volume.

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AbstractÐNanoindentation for measuring thin ®lm mechanical properties is probably the most popular yet ill-understood method due to its inherent complexities. As opposed to burst pressure or microtensile tests of lithographed structures, where relatively uniform stress ®elds may be generated, the indentation-induced stress gradients can produce unique challenges. Because of the test's simplicity and ability to mechanically probe the smallest of scales, it is becoming increasingly applied. Five possible stages of deformation are suggested from Hertzian elastic to ®lm delamination and double buckling. In particular metal ®lms on harder substrates are emphasized where it is shown that dislocation nucleation and arrest are only partially understood. Later stages of ®lm delamination are illustrated with Cu/SiO 2 /Si where it is shown that the true work of adhesion is 0.6 J/m 2 . Current limitations of indentation-induced delamination measures of toughness involve large scatter associated with sensitivity of the fracture radius to the contact radius ratio.

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