AbstractThe structure and properties of a preimidized photosensitive polyimide (Probimide PSPI, a copolyimide of benzophenonetetracarboxylic dianhydride with alkyl groups substituted aromatic diamines) were studied with variations of UV exposure energy and bake temperature by means of wide angle X‐ray diffraction, dynamic mechanical thermal analysis, stress‐strain analysis, and residual stress analysis. The X‐ray diffraction patterns patterns indicate that the PSPI is amorphous in the solid state. The Tg was 378°C ∼ 410°C, depending upon the thermal history over the range of 350°C ∼ 400°C. At the glass transition region, the dynamic storage modulus E′ was very sensitive to both i‐line exposure energy and thermal history. However, the mechanical stress‐strain behavior at room temperature was primarily dependent on the thermal history. The mechanical properties were 2.6 GPa ∼ 2.9 GPa Young's modulus, 131 MPa ∼ 168 MPa tensile strength, 10% ∼ 12% yield strain, and 16% ∼ 74% elongation at break, depending upon the baking or annealing. These dynamic and static mechanical properties indicate that on the PSPI backbone, crosslinks are formed thermally as well as photochemically. The thermal crosslinks might be formed through thermal liberation of the labile alkyl groups of aromatic diamine moieties and subsequent coupling of the radicals. The thermal degradation was also evidenced in the mechanical properties degraded by baking above 375°C or annealing above 350°C. In addition, during baking and cooling, the residual stress was dynamically measured on Si wafers as a function of temperature. The stress at room temperature was 48 MPa ∼ 52 MPa for the PSPI films baked at 350°C or 400°C, regardless of i‐line exposure.