Determining Pore Structure and Growth Mechanisms in Templated Nanoporous Low-k Films

Templating is one of the most popular methods for generating nanocomposite and nanoporous films and the resultant pore size and pore interconnection length depend strongly on porogen concentration/porosity among other factors. Positronium Annihilation Lifetime Spectroscopy (PALS) analysis has been performed on a series of films produced using increasing concentrations of a type of cyclodextrin (CD) porogen in a modified silsesquioxane host matrix. PALS reveals the relationship between the resulting pore structure (both size and interconnection length) and porosity, which can be used to deduce pore shape. At low porogen concentration, isolated pores are resolved, but the pore size is consistent with a cluster of two or three CD molecules, rather than an individual one. As the porosity increases, the aggregation of the porogen domains appears to be more 3-dimensional (pseudo-random) with gradual increase in pore size. Computer simulations using a random pore growth model show consistent trends for pore size growth, but the agreement is poor for interconnection length. It is a key demonstration of the usefulness of PALS in untangling the fundamental pore structure and its evolution in porosity. PALS characterization of porosity provides novel feedback in the understanding and design of nanoporous materials.

Depth-profiling Pore Morphology in Nanoporous Thin Films Using Positronium Lifetime Annihilation Spectroscopy

Positronium annihilation lifetime spectroscopy (PALS) using a positron beam is a proven technique to characterize porosity in amorphous thin film materials. The capability to control the depth of the implanted positrons is unique to beams as compared to traditional bulk PALS techniques. By increasing the positron beam energy, positrons are implanted deeper into the film. Control of the positron implantation depth in beam-PALS allows analysis of sub- micron films, investigation of depth-dependent film inhomogeneities, determination of pore interconnection lengths, and access to buried films under barrier layers. Details on PALS depth profiling and an example of applying the technique to a plasma-enhanced-chemical-vapor- deposited (PECVD) porous film are presented.

Electrical, Mechanical, and Structural Properties of Fluoro-Containing Poly(silsesquioxanes) Based Porous Low k Thin Films

Low dielectric fluoro-containing poly(silsesquioxanes) (PSSQs) have been synthesized using trifluoropropyl trimethoxysilane (TFPTMS), methyl trimethoxysilane (MTMS), and 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetra(trimethoxysilylethyl) cyclotetrasiloxane. The properties of fluorocontaining PSSQs based thin films were studied by electrical, mechanical, and structural characterization. Film was spun on a silicon substrate, baked at 150°C and 250°C for 1 minute, respectively, and cured in the furnace at 420°C for 1 hour under vacuum condition. Thermally decomposable trifluoropropyl groups of the fluoro-containing PSSQ were served as a pore generator and partially contributed to lower a dielectric constant. â-cyclodextrin (CD) was also employed as a pore generator. The concentration of the pore generator in the film was varied from 0 to 30 %. The dielectric constants of the porous PSSQ films were found to be in the range of 2.7 – 1.9 (at 100 kHz). Hardness and Young's modulus of the films were measured by nano-indentation. The elastic modulus and hardness of the porous films were well correlated with the concentration of the pore generators. Positronium Annihilation Lifetime Spectroscopy (PALS) was employed to characterize a pore size of the porous fluoro-containing PSSQ film. The pore size of the film was less than 2.2 nm. The nanoporous films showed quite promising properties for commercial application.