Low dielectric constant (low-k) films have been widely used as insulating materials in ultra-large-scale integrated circuits. Low-k films receive heavy damage during the plasma processes of etching or ashing, resulting in an increase in their dielectric constant. In order to realize damage-free plasma processes for low-k films, it is essential to determine the influence of radiation, radicals, and ions emitted in the plasma process on the characteristics of low-k films. We have developed a technique to evaluate the influence of radiation, radicals, ions, and their synergies on films in real plasma processes and have named it pallet for plasma evaluation (PAPE). Using the PAPE, plasma-induced damage on porous SiOCH films were investigated in dual-frequency capacitively coupled H2∕N2 plasmas. The damage was characterized by ellipsometry, Fourier-transform infrared spectroscopy, and thermal desorption spectroscopy. On the basis of the results, the damage mechanisms associated with vacuum ultraviolet (VUV) and UV radiation, radicals, and ions were clarified. The damage was caused not only by ions and radicals but also by VUV and UV radiation emitted by the plasmas. Moreover, it was found that the synergy between the radiation and the radicals enhanced the damage.
An organic low-dielectric constant (low-k) film, polyallylene (PAr), is a prospective candidate for low-k interlayer films for ultra large-scale integrated circuits (ULSIs). PAr films are caused the property changes such as increases of the dielectric constant during plasma etching and ashing. In a previous study, we have developed a novel technique called pallet for plasma evaluation (PAPE) for separately evaluating the property changes caused by radiation, radicals, and ions in process plasmas and clarified the mechanism of plasma-induced property changes on low-k porous SiOCH films. In this study, using the PAPE technique, we investigated the changes on the surface of a PAr film due to radiation, radicals, radiation with radicals, and ions in dual-frequency capacitively coupled H2/N2 plasmas. The property changes were characterized by ellipsometry and X-ray photoelectron spectroscopy. The property changes on the PAr films due to radiation and radicals were considerably smaller compared to those on the low-k porous SiOCH films.
We investigated the relationship between the hard mask faceting that occurs during organic low-k etching and the ion energy distribution function of a capacitively coupled plasma reactor. We minimized the hard mask faceting by precisely controlling the ion energy. This precise control was obtained by selecting the optimum bottom frequency and bias power. We measured the amount of damage done to a SiOCH film exposed to H2∕N2 plasma in order to find the H2∕N2 ratio at which the plasma caused the least damage. The amount of moisture uptake by the damaged SiOCH film is the dominant factor controlling the dielectric constant increase (Δk). To suppress Δk, the incident ion species and ion energies have to be precisely controlled. This reduces the number of adsorption sites in the bulk SiOCH and maintains the hydrophobic surface that suppresses water permeation during air exposure.
In the 21st century, the optical computation is likely to be the basic technology for processing lots of information at high speed. The aim of the present research work is to develop optical logic gates or memory chips. For this purpose, we have examined the suitability of organic nonlinear optical dye material Vanadyl-phthalocyanine (VOPc). Large single crystals of this material have been fabricated by using Molecular Beam Epitaxy (MBE) technique. The epitaxial films were formed on the substrate under optimum operating conditions. However, the epitixial growth is observed only up to a limited thickness. Above this thickness, the films become non-epitaxial, which can be improved by annealing. The reformation of the epitaxial films has been confirmed. We have also reported the effects of the environment of high temperature on the multilayered tetra-tert-butyl-Vanadyl-phthalocyanine ((t-bu)4VOPc) films, formed by Langmuir-Blodgett (LB) method. The solvent used to dissolve ((t-bu)4VOPc) was 1,2-dichloroethane. The monolayer on the surface of the water was transferred to a glass substrate by the vertical dipping method. If the multilayered stack is too thick, the molecular arrangement of the film may get disturbed. The improvement in the molecular arrangement of the LB films was examined and confirmed by measuring it’s nonlinear optical susceptibility, using Maker Fringe Method. Monolayer formation on water surface depends on the surface pressure-area isotherm. If this monolayer formation is not perfect, multiplayer stacks cannot be formed. The molecular films were aligned almost perpendicular to the substrate, as estimated from the limiting molecular area of surface pressure-area isotherm. The molecular organization of the monolayer on the substrate and the molecular structure of the multilayered ((t-bu)4VOPc) films are discussed.
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