Surface and grain boundary electron scattering contribute significantly to resistivity as the dimensions of polycrystalline metallic conductors are reduced to, and below, the electron mean free path. A quantitative measurement of the relative contributions of surface and grain boundary scattering to resistivity is very challenging, requiring not only the preparation of suitably small conductors having independent variation of the two relevant length scales, namely, the sample critical dimension and the grain size, but also independent experimental quantification of these two length scales. In most work to date the sample grain size has been either assumed equal to conductor dimension or measured for only a small number of grains. Thus, the quantification of the classical size effect still suffers from an uncertainty in the relative contributions of surface and grain boundary scattering. In this work, a quantitative analysis of both surface and grain boundary scattering in Cu thin films with independent variation of film thickness (27 nm to 158 nm) and grain size (35 nm to 425 nm) in samples prepared by sub-ambient temperature film deposition followed by annealing is reported. Film resistivities of carefully characterized samples were measured at both room temperature and at 4.2 K and were compared with several scattering models that include the effects of surface and grain boundary scattering. Grain boundary scattering is found to provide the strongest contribution to the resistivity increase. However, a weaker, but significant, role is also observed for surface scattering. Several of the published models for grain boundary and surface scattering are explored and the Matthiessen's rule combination of the Mayadas and Shatzkes' model of grain boundary scattering and Fuchs and Sondheimer's model of surface scattering resistivity contributions is found to be most appropriate. It is found that the experimental data are best described by a grain boundary reflection coefficient of 0.43 and a surface specularity coefficient of 0.52. This analysis finds a significantly lower contribution from surface scattering than has been reported in previous works, which is in part due to the careful quantitative microstructural characterization of samples performed. The data does suggest that there is a roughness dependence to the surface scattering, but this was not conclusively demonstrated. Voids and impurities were found to have negligible impact on the measured resistivities of the carefully prepared films.

With continued shrinking of CMOS technology to reduce the gate delay times, an increase in the resistivity of the metal corresponding to the wire dimension is a concern. This phenomenon of increase in resistivity with decreasing dimension of the thin metallic film or interconnect is known as the "classical size effect". Various theories have been postulated to explain the phenomenon of classical size effect; these theories can be broadly classified as resistivity due to scattering arising from surface and grain boundaries. The total resistivity of metals depends on the electron scattering due to impurities, phonons, surfaces, grain boundaries, and other crystal defects. Managing the size effect in a practical and manufacturing way is of major concern to the microelectronics industry. Since each of the processes (phonon, surface and grain boundary scattering) adds to the resistivity and are interrelated, it further complicates managing the size effect. However, these effects have been separately studied. In this work, the effect of annealing on the classical size effect in Cu thin films deposited on SiO2 substrate is investigated. Polycrystalline Cu thin films having thicknesses in the range of 10nm to 200nm were ultra high vacuum sputter deposited on thermally grown SiO2 surfaces. The films were annealed at temperatures in the range of 150°C to 800°C in argon and argon+3% hydrogen gases. The un-annealed Cu thin films exhibit higher resistivity than the annealed films. The resistivities of un-annealed films were in good agreement with Mayadas and Shatzkes model. When annealed the films undergoes grain growth resulting in lowering the resistivities by about 20%-30% thereby confirming the role of grain size on resistivity of the film. However, there is a limit to annealing, i.e. agglomeration phenomenon. Agglomeration is a thermally activated process resulting in a reduction of the free energy of the film–substrate system and can occur well below the melting point of the material by surface and interfacial diffusion. The reduction of film-substrate interfacial energy, film-surface interfacial energy and stresses within the film are possible driving forces for agglomeration. This work also includes the study of agglomeration phenomenon. The agglomeration behavior of Cu is investigated and compared with that of Ru, Au and Pt thin films with thicknesses in the range of 10 nm to 100 nm UHV deposited on thermally grown SiO2 substrate. The films were annealed at temperatures in the range of 150°C to 800°C in argon and argon+3% hydrogen gases. Scanning electron microscopy was used to investigate the agglomeration behavior, and transmission electron microscopy was used to characterize the microstructure of the as-deposited and annealed films. The agglomeration sequence in all the films is found to follow a two step process of void nucleation and void growth. However, void growth in Au and Pt thin films is different from Cu and Ru thin films. Residual stress and adhesion were observed to play important part in deciding the mode of void growth in Au and Pt thin films. Lastly, it is also observed that the tendency for agglomeration can be reduced by encapsulating the metal film with an oxide overlayer, which in turn improves the resistivity of the thin film due to prolonged grain growth without film breakup.