Influence of molecular weight and film thickness on the glass transition temperature and coefficient of thermal expansion of supported ultrathin polymer films

• Published in: Thin solid films 2004-02, Vol.449 (1), p.231-241
• Main Authors: Singh, Lovejeet, Ludovice, Peter J., Henderson, Clifford L.
• Format: Article
• Language: English
• Subjects: Condensed matter: structure, mechanical and thermal properties; Ellipsometry; Equations of state, phase equilibria, and phase transitions; Exact sciences and technology; Glass transition temperature; Glass transitions; Physics; Polymer thin films; Polystyrene; Specific phase transitions; Thermal expansion; thermomechanical effects; Thermal expansion; thermomechanical effects and density; Thermal properties of condensed matter; Thermal properties of crystalline solids
• ISSN: 0040-6090; 1879-2731
• DOI: 10.1016/S0040-6090(03)01353-1

The influence of film thickness and molecular weight on the glass transition temperature and coefficient of thermal expansion for polystyrene thin films supported on silicon native oxide surfaces has been studied in detail using variable angle spectroscopic ellipsometry. It was observed that T g exhibits a dependence on both film thickness and polymer molecular weight. The T g of polystyrene was found to decrease with decreasing film thickness below a critical film thickness of approximately 10 times the polymer radius of gyration. The coefficient of thermal expansion was also found to increase sharply as film thickness is decreased below approximately 10 times the polymer radius of gyration. It was found that the T g of polystyrene thin films supported on silicon native oxide surfaces can be modeled using a ‘master’ curve based on reduced thickness (i.e. thickness relative to the polymer radius of gyration) and reduced glass transition temperature (i.e. T g relative to the polymer bulk T g). Using this concept, a single equation has been generated that describes the dependence of T g on molecular weight and film thickness for the polystyrene on silicon native oxide system.