Intrinsically Negative Photosensitive Polyimides with Enhanced High-Temperature Dimensional Stability and Optical Transparency for Advanced Optical Applications via Simultaneous Incorporation of Trifluoromethyl and Benzanilide Units: Preparation and Properties.

Negative photosensitive polyimides (PSPIs) with the photo-patterned ability via the photocrosslinking reactions induced by the i-line (365 nm) and h-line (426 nm) emitting wavelengths in high-pressure mercury lamps have been paid increasing attention in semiconductor fabrication, optical fiber communications, and other advanced optoelectronic areas. In the current work, in view of the optical and thermo-mechanical disadvantages of the currently used negative PSPIs, such as the intrinsically photosensitive or auto-photosensitive systems derived from 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and the ortho-alkyl- substituted aromatic diamines, a series of modified negative PSPIs with the enhanced optical transparency in the wavelength of 365~436 nm and apparently reduced coefficients of linear thermal expansion (CTE) were developed. For this purpose, a specific aromatic diamine with both of trifluoromethyl and benzanilide units in the molecular structures, 2,2'-bis(trifluoromethyl)-4,4'-bis[4-(4-amino-3-methyl)benzamide]biphenyl (MABTFMB) was copolymerized with BTDA and the standard 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane (TMMDA) diamine via a two-step chemical imidization procedure. As compared with the pristine PI-1 (BTDA-TMMDA) system, the new-developed fluoro-containing PSPI systems (FPI-2~FPI-7) exhibited the same-level solubility in polar aprotic solvents, including N-methyl-2-pyrrolidone (NMP) and N,N- dimethylacetamide (DMAc). The FPI films cast from the corresponding FPI solutions in NMP showed the optical transmittances of 78.3-81.3% at the wavelength of 436 nm (T436, h-line), which were much higher than that of the PI-1 (T436 = 60.9%). The FPI films showed the CTE values in the range of 40.7 × 10-6/K to 54.0 × 10-6/K in the temperature range of 50 to 250 °C, which were obviously lower than that of PI-1 (CTE = 56.5 × 10-6/K). At last, the photosensitivity of the FPI systems was maintained and the micro-pattern with the line width of 10 µm could be clearly obtained via the standard photolithography process of FPI-7 with the molar ratio of 50% for MABTFMB in the diamine moiety.