RESUMEN
The formation of polymeric micro-patterns on various substrates via a photolithography procedure has been widely used in semiconductor fabrication. Standard polymer patterns are usually fabricated via photosensitive polymer varnishes, in which large amounts of potentially harmful solvents with weight ratios over 50 wt% have to be removed. In the current work, a novel pattern-formation methodology via solvent-free electrospun photosensitive polymeric fibrous membranes (NFMs) instead of the conventional photosensitive solutions as the starting photoresists was proposed and practiced. For this purpose, a series of preimidized negative auto-photosensitive polyimide (PSPI) resins were first prepared via the two-step chemical imidization procedure from the copolymerization reactions of 3,3',4,4'-benzophenonetetracarboxylic- dianhydride (BTDA) and two ortho-methyl-substituted aromatic diamines, including 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane (TMMDA) and 3,7-diamino-2,8-dimethyl- dibenzothiophene sulfone (TSN). The derived homopolymer PI-1 (BTDA-TMMDA) and the copolymers, including SPI-2~SPI-6, with the molar ratio of 5~25% for TSN in the diamine units, showed good solubility in polar solvents. Then, a series of PSPI NFMs were fabricated via standard electrospinning procedure with the developed PSPI solutions in N,N-dimethylacetamide (DMAc) with a solid content of 25 wt% as the starting materials. The derived PSPI NFMs showed good thermal stability with 5% weight loss temperatures higher than 500 °C in nitrogen. Meanwhile, the derived PSPIs showed good photosensitivity to the ultraviolet (UV) emitting wavelengths of i-line (365 nm), g-line (405 nm) and h-line (436 nm) of the high-pressure mercury lamps in both forms of transparent films and opaque NFMs. Fine micro-patterns with a line width of around 100 µm were directly obtained from the representative SPI-4 NFM via standard photolithography procedure.
RESUMEN
Optically transparent polymer films with excellent thermal and ultraviolet (UV) resistance have been highly desired in advanced optoelectronic fields, such as flexible substrates for photovoltaic devices. Colorless and transparent polyimide (CPI) films simultaneously possess the good thermal stability and optical transparency. However, conventional CPI films usually suffered from the UV exposure and have to face the deterioration of optical properties during the long-term service in UV environments. In the current work, the commercially available hindered amine light stabilizers (HALS) were tried to be incorporated into the semi-alicyclic CPI matrix with the aim of enhancing the UV exposure stability. For this target, a CPI-0 film was first prepared from hydrogenated pyromellitic dianhydride (HPMDA) and 2,2'-dimethylbenzidine (DMBZ) via a one-step polycondensation procedure. Then, the commercially available HALS were incorporated into the CPI-0 (HPMDA-DMBZ) film matrix to afford four series of CPI/HALS composite films. Experimental results indicated that the Tinuvin® 791 HALS showed the best miscibility with the CPI-0 film matrix and the derived CPI-D series of composite films exhibited the best optical transmittances. The CPI-D nanocomposite films showed apparently enhanced UV exposure stability via incorporation of the 791 additives. For the pristine CPI-0 film, after the UV exposure for 6 h, the optical properties, including the transmittance at the wavelength of 350 nm (T350), lightness (L*), yellow indices (b*), and haze obviously deteriorated with the T350 values from 55.7% to 17.5%, the L* values from 95.12 to 91.38, the b* values from 3.38 to 21.95, and the haze values from 1.46% to 9.33%. However, for the CPI-D-10 film (791: CPI-0 = 1.0 wt%, weight percent), the optical parameters were highly maintained with the T350 values from 61.4% to 53.8%, the L* values from 95.46 to 95.36, the b* values from 1.84 to 1.51, and the haze values from 0.69% to 3.34% under the same UV aging conditions.
