Characterization of porous low-k films using variable angle spectroscopic ellipsometry

doi:10.1063/1.2189018Variable angle spectroscopic ellipsometry (VASE™) is used as a tool to characterize properties such as optical constant, thickness, refractive index depth profile, and pore volume fraction of single and bilayer porous low-k films. The porous films were prepared using sacrificial pore generator (porogen) approach. Two sets of porous films with open- and closed-pore geometries were measured. Three models were used for data analysis: Cauchy, Bruggeman effective medium approximation (BEMA), and graded layer. Cauchy, a well-known model for transparent films, was used to obtain thickness and optical constant, whereas BEMA was utilized to calculate the pore volume fraction from the ellipsometric data. The Cauchy or BEMA models were then modified as graded layers, resulting in a better fit and a better understanding of the porous film. The depth profile of the porous film implied a more porous layer at the substrate-film interface. We found 3%-4% more porosity at the interface compared with the bulk for both films. This work shows that VASE™, a nondestructive measurement tool, can be used to characterize single- and multigraded layer porous films quickly and effectively.The authors would like to acknowledge the financial support of Semiconductor Research Corporation (SRC)

EFFECT OF PRECURSOR HISTORY ON RESIDUAL-STRESS AND RELAXATION BEHAVIOR OF HIGH-TEMPERATURE POLYIMIDES

Using a wafer bending technique, residual stress and its relaxation were investigated for four different kinds of high temperature polyimides: rodlike PMDA-PDA, semi-rigid BPDA-PDA, semi-flexible PMDA-ODA, and flexible BTDA-ODA. Residual stress was measured in situ on silicon wafers during thermal imidization of the polyimide precursors and subsequent cooling of the resulting polyimides as a function of temperature over the range of 25-400-degrees-C. The stress of the cured films at room temperature was significantly relaxed by the moisture uptake of the films rather than their creep behaviour. Both residual stress and moisture-induced stress relaxation in the cured polyimide films were strongly dependent upon the molecular nature (that is, molecular chain rigidity, degree of molecular orientation and packing), as well as the precursor origin. In addition, the diffusion coefficients of water in the cured polyimide films were estimated by best-fitting stress relaxation against time profiles.X1143sciescopu

STRUCTURE AND PROPERTIES OF THIN-FILMS OF BINARY RODLIKE FLEXIBLE POLYIMIDE MIXTURES

Binary mixtures of a rodlike poly(p-phenylene pyromellitimide) (PMDA-PDA) and a flexible 6F-BDAF polyimide synthesized from hexafluoroisopropylidene diphthalic anhydride and 2,2-bis (4-aminophenoxy-p-phenylene) hexafluoropropane were prepared by solution-blending of the meta-PMDA-PDA poly (amic ethyl ester) and 6F-BDAF poly (amic acid) precursors, followed by solvent evaporation and thermal imidization. Mixtures containing different molecular weights of 6F-BDAF poly(amic acid) were studied. The size scale of the phase separation, as measured by light scattering, is ca. 1-mu-m or smaller in most cases. The domain size is primarily set by the demixing of the precursor polymers during solvent evaporation, with no significant coarsening observed during the thermal imidization. The observed variation of the domain size with molecular and process parameters such as composition, molecular weight, and film thickness is discussed in terms of the miscibility of the precursor polymers, rate of solvent evaporation, and solidification. Dynamic mechanical thermal analysis and dielectric relaxation measurements indicate that the glass transition temperature of 6F-BDAF is unaffected in all of the mixtures studied, indicating complete demixing of rodlike and flexible polyimides in agreement with theory. X-ray photoelectron spectroscopy results show a strong surface segregation of 6F-BDAF in mixtures containing as low as 10% by weight of the 6F-BDAF component in the bulk. The mixtures with PMDA-PDA as the major matrix component therefore exhibit excellent mechanical toughness, dimensional stability up to 500-degrees-C, low coefficients of thermal expansion (< ca. 10 ppm/degrees-C), and low dielectric constants (< 3.0). On the other hand, the surface properties of the mixtures are dominated by the flexible 6F-BDAF, resulting in excellent polymer/polymer self-adhesion (lamination) properties between fully imidized films.X1144sciescopu

The efficacy of post porosity plasma protection against vacuum-ultraviolet damage in porous low-k materials

International audienc

Toward Successful Integration of Porous Low-k Materials: Strategies Addressing Plasma Damage

International audienc