T. Rajagopalan

Low temperature deposition of nanocrystalline silicon carbide films by plasma enhanced chemical vapor deposition and their structural and optical characterization

Nanocrystalline silicon carbide (SiC) thin films were deposited by plasma enhanced chemical vapor deposition technique at different deposition temperatures (Td) ranging from 80 to 575 °C and different gas flow ratios (GFRs). While diethylsilane was used as the source for the preparation of SiC films, hydrogen, argon and helium were used as dilution gases in different concentrations. The effects of Td, GFR and dilution gases on the structural and optical properties of these films were investigated using high resolution transmission electron microscope (HRTEM), micro-Raman, Fourier transform infrared (FTIR) and ultraviolet-visible optical absorption techniques. Detailed analysis of the FTIR spectra indicates the onset of formation of SiC nanocrystals embedded in the amorphous matrix of the films deposited at a temperature of 300 °C. The degree of crystallization increases with increasing Td and the crystalline fraction (fc) is 65%±2.2% at 575 °C. The fc is the highest for the films deposited with hydrogen d...

Low-k organosilicate films prepared by tetravinyltetramethylcyclotetrasiloxane

Low-k films with k of 2.5–2.9 were deposited under different conditions of pressures and temperatures using a plasma-enhanced chemical vapor deposition (PECVD) system. These films were prepared using a new liquid precursor, tetravinyltetramethylcyclotetrasiloxane (TVTMCTS) and H2 carrier gas. The rf power was kept as low as possible to maintain the original ring structure in the films. The as-deposited films were annealed and the dielectric and optical properties were investigated. Identification of the absorption bands in the IR spectra for as-deposited films reveals a broadband around 950–1200 cm−1 arising from the Si–O stretching mode of the ring (1065 cm−1) and chain structure (1000 cm−1), respectively; a band at 750–900 cm−1 due to Si–O bending (790 cm−1); Si–CH3 rocking mode (760 cm−1); a sharp band centered at 1260 cm−1 due to a Si–CH3 bending mode; and a broadband at 2800–3000 cm−1 due to the CH group. A comparison of the IR spectra of the PECVD film and TVTMCTS liquid reveals that vinyl vibration...

Supercritical carbon dioxide extraction of porogens for the preparation of ultralow-dielectric-constant films

Supercritical carbon dioxide extraction of poly(propylene glycol) porogen from poly(methylsilsesquioxane) (PMSSQ) cured to temperatures adequate to initiate matrix condensation, but still below the decomposition temperature of the porogen, is demonstrated to produce nanoporous, ultralow-dielectric-constant thin films. Both closed and open cell porous structures were prepared simply by varying the porogen load in the organic/inorganic hybrid films. 25 and 55 wt % porogen loads were investigated in the present work. Structural characterization of the samples conducted using transmission electron microscope, small angle x-ray scattering, and Fourier transform infrared spectroscopy, confirms the extraction of the porogen from the PMSSQ matrix at relatively low temperatures (⩽200 °C). The standard thermal decomposition process is performed at much higher temperatures (typically in the range of 400 °C–450 °C). The values of dielectric constants and refractive indices measured are in good agreement with the stru...

Supercritical carbon dioxide extraction to produce low-k plasma enhanced chemical vapor deposited dielectric films

A treatment to reduce the dielectric constant of plasma enhanced chemical vapor deposition (PECVD) films is presented. The method involved extracting low molecular weight or CO2 soluble species in the films by post deposition supercritical CO2 pressurization (SCCO2). We observed a decrease in k value of about 10%–14% in a composite film of organosilicate and a-C:F after SCCO2 treatment at 200 °C for 8 h. The composite films were deposited by PECVD using C4F8 and tetravinyltetramethylcyclotetrasiloxane (TVTMCTS) liquid source and H2 carrier gas at room temperature. As-deposited films were also annealed at 200 °C for 8 h in N2 atmosphere to compare the effect of thermal annealing without SCCO2 treatment. The result shows that there is no change in the k of the films after annealing. Thus, SCCO2 extraction is a good method for reducing the dielectric constant of these PECVD composite films. Supercritical CO2 pressurization of the film deposited using TVTMCTS and H2 only without the addition of C4F8 has no ef...

Supercritical CO2 Extraction of Porogen Phase: An Alternative Route to Nanoporous Dielectrics

We present a supercritical CO{sub 2} (SCCO{sub 2}) process for the preparation of nanoporous organosilicate thin films for ultra low dielectric constant materials. The porous structure was generated by SCCO{sub 2} extraction of a sacrificial poly(propylene glycol) (PPG) from a nanohybrid film, where the nanoscopic domains of PPG porogen are entrapped within the crosslinked poly(methylsilsesquioxane) (PMSSQ) matrix. As a comparison, porous structures generated by both the usual thermal decomposition (at ca. 450 C) and by a SCCO{sub 2} process for 25 wt% and 55 wt% porogen loadings were evaluated. It is found that the SCCO{sub 2} process is effective in removing the porogen phase at relatively low temperatures (< 200 C) through diffusion of the supercritical fluid into the phase-separated nanohybrids and selective extraction of the porogen phase. Pore morphologies generated from the two methods are compared from representative three-dimensional (3D) images built from small angle x-ray scattering (SAXS) data.

Creating Nanoporosity by Selective Extraction of Porogens Using Supercritical Carbon Dioxide/Cosolvent Processes

This work presents a novel approach using supercritical carbon dioxide (SCCO 2 ) to selectively extract poly(propylene glycol) (PPG) porogen from a poly(methylsilsesquioxane) (PMSSQ) matrix, which results in the formation of nanopores. Nanoporous thin films were prepared by spin-casting a solution containing appropriate quantities of PPG porogen and PMSSQ dissolved in PM acetate. The as-spun films were thermally cured at temperatures well below the thermal degradation temperature of the organic polymer to form a cross-linked organic/inorganic polymer hybrid. By selectively removing the CO 2 soluble PPG porogen, open and closed pore structures are possible depending upon the porogen load and its distribution in the matrix before extraction. In the present work, two different loadings of PPG namely 25 wt.% and 55 wt.% were used. Both static SCCO 2 and pulsed SCCO 2 /cosolvent treatments were used for PPG extraction. The initial results indicate that the pulsed SCCO 2 /cosolovent treatment was more efficient. Fourier transform infrared spectroscopy (FTIR) and refractive index measurements further corroborate the successful extraction of the porogens at relatively low temperatures (2000C). For the pure PMSSQ film, the k value is 3.1, whereas it is 1.46 and 2.27 for the open and closed pore compositions respectively after the static SCCO 2 extraction and 430°C subsequent annealing. The reduction in the k-value is attributed to the formation of nanopores. The pore structure was verified from transmission electron microscopy (TEM), and from small-angle x-ray scattering (SAXS) measurements, the pore size was determined to be 1-3 nm for these films.