| Positrounium annihilation lifetime spectroscopy (PALS) utilizing a focused low energy beam of positrons to control implantation depth enables the analysis of very thin films. Beam-PALS was used to study confinement and interfacial effects on polymer mobility in ultra-thin polycarbonate films and to characterize nanoporous structures of polymeric low dielectric constant (low-k ) thin films.; Three complementary techniques were used to address the apparent discrepancies in recent polymer film results. Beam-PALS (probing positronium nanovoid lifetime, tau), specular X-ray reflectivity (SXR, monitoring film thickness, h) and incoherent neutron scattering (INS, characterizing mean-square atomic displacements, <u2>) were combined to study the thermophysical properties of Bisphenol-A polycarbonate (PC) ultra-thin films (60 A to ∼1000 A) supported on an oxidized silicon wafer surface. As h decreased the concomitant reduction in thermal expansion coefficients of h, tau and < u2>, as well as the decreased amplitudes of < u2>, indicated that thin film confinement produces suppressed molecular mobility in PC. These films were modeled with an immobile interface layer ranging from 38 A to 130 A, depending on the measurement technique and the temperature range. No clear trends in the apparent glass transition temperature (Tg) emerged from these techniques, thus rendering Tg shifts inconclusive and of less fundamental importance.; Beam-PALS was also applied to characterize several generations of porous SiLK (Trade Mark of Dow Chemical) low-k films to reveal the size, size distribution, interconnectivity and possible morphology of the engineered nanopores. The dependence of these properties on porogen loading/porosity was carefully analyzed and compared, when possible, with results from other techniques such as small-angle X-ray scattering and AFM. Unique to the PALS technique is the ability to quantify the pore interconnection length. Porous SiLK (V9), U.2 and Y were found to have progressively smaller pores, (from ∼5 nm in diameter to less than 2 nm) with shorter interconnection length. The observed pore structure evolution with processing temperature further demonstrates the capability of PALS in monitoring the fabrication and integration of porous low-k materials. The concomitant improvement of pore characterization techniques is an essential and enabling aspect of meeting future low- k materials and integration challenges. |
