Published online by Cambridge University Press: 01 February 2011
A high-temperature nanoindentation measurement method has been developed for evaluating the hardness and modulus of low-k films when the temperature is raised from R.T. to 200°C. Thermal stability and chemical changes due to heating were investigated by Raman spectroscopy, Fourier transform infrared spectroscopy and thermogravimetry-differential thermal analysis, and by thermal desorption spectroscopy, respectively. Two different classes of low-k materials, organic polyarylence ether film and methyl-hydrogen-silsesquioxane film, were examined. The hardness and modulus of the former film during heating increased due to water desorption in the lower temperature range, and then decreased due to the evolution of hydrocarbon gas from some unreacted components or solvent residuals in the higher temperature range. In regard to the latter film, the hardness and modulus of a specimen (A) having a higher hydrocarbon content decreased during heating and reached the lowest value at 200°C and then constantly remained at the lowest levels during cooling. In contrast, no significant changes in hardness and modulus were observed for a specimen (B) having a lower hydrocarbon content in either the heating or cooling process. The reduction of the hardness and modulus of specimen A was attributed to thermal decomposition of most of its Si-CH3 and SiH/SiH2 chains. These results revealed that the temperature dependence of the hardness and modulus of low-k films is significantly affected by physical and/or chemical changes during heating due to moisture absorption, thermal evolution of organic residuals and thermal decomposition, rather than other factors such as thermal stress.