Stress in polyimide coatings

Abstract

AbstractThe effect of film thickness on in‐plane molecular orientation and stress in polyimide films prepared from pyromellitic dianhydride with 4,4′‐oxydianline was investigated using a prism coupling technique to measure the refractive index. Film thickness was controlled by varying both solution concentration and spinning conditions. Birefringence, the difference between the in‐plane and out‐of‐plane refractive indices, was used to characterize the in‐plane molecular orientation. The observed birefringence is a combination of the birefringence resulting from molecular orientation and the birefringence induced by the residual stress present in the films. The birefringence decreases with increasing film thickness over the range of thicknesses studied (3–20 μm) indicating that the molecular orientation decreases with increasing film thickness. The in‐plane coefficient of linear thermal expansion (CTE), controlled by the level of orientation in the film, increases from 18 to 32 × 10−6/°C over the same thickness range. The birefringence of free‐standing films was lower than that of adhered films due to the release of residual stress in the film once the film is removed from the substrate. The residual film stress arises primarily from the mismatch in CTEs between the polyimide film and the substrate to which the film is adhered. Thus, since the film anisotropy decreases with increasing thickness, the film stress increases with increasing thickness. Residual stress calculated by integrating the product of the film modulus and the CTE mismatch assuming temperature‐dependent properties is comparable to experimentally measured film stress. Ignoring the temperature dependence of the film properties leads to an overestimation of stress. Moisture uptake was used to study the stress dependence of the optical properties. Moisture uptake increases both the in‐plane and out‐of‐plane refractive indices by equal amounts in free‐standing films due to an isotropic increase in the polarizability. In adhered films, an increase in moisture uptake leads to a decrease in the birefringence due to a swelling‐induced decrease in the residual film stress. © 1994 John Wiley & Sons, Inc.