Photocrosslinkable nonlinear optical polymers and directly-patternable polyimide dielectrics



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The development of high-efficiency nonlinear optical (NLO) polymers has opened up many opportunities in the field of electro-optics. However, current NLO polymers do not meet stability requirements for semiconductor integration. In an effort to improve this, we examined the effects of crosslinking following electric field poling. A series of photocrosslinkable polymers bearing side chain chromophores was synthesized, poled and evaluated on the basis of the thermal stability of Second Harmonic Generation. Photoinitiation allowed for control of the onset of curing. Crosslinking was monitored by FTIR and optimal conversion was achieved by applying a slow temperature ramp during exposure. The ultimate stability of the poled polymers was directly related to the number of crosslinking substituents attached to the chromophore pendant group. With two reactive groups per chromophore significant SHG was retained at temperatures beyond the polymer Tg.

In integrated circuit packaging there is a need for directly-patternable polymers of low dielectric constant. Bridging the gap between the high-value silicon chip and circuit board is a substrate comprising alternating layers of metal conductor and polymer dielectric. PMDA-ODA, an aromatic polyimide, meets many of the requirements for integration and can be patterned using a photobase generator (PBG). Due to absorbance by the PMDA-ODA precursor, this PBG must have activity at visible wavelengths. Several oxime urethanes were synthesized and evaluated as candidate long wavelength PBG. These compounds exhibit clean photochemistry and high visible light sensitivity. Unfortunately, carbamate thermal stability is insufficient for patterning PMDA-ODA.

For improved material properties, PMDA-TFMB, a fluorinated polyimide, was also evaluated. Importantly, the polymer precursor is sufficiently transparent to employ thermally-stable near-UV photobases. With photobase, 2.5 micron features were resolved in PMDA-TFMB. An ancillary benefit of this methodology is reduced cure temperature (~200 °C), a traditional drawback of polyimides. This material demonstrates a dielectric constant near 3 and a thermal expansion coefficient (CTE) of approximately 6 ppm/°C in-plane. Through-plane thermal expansion is somewhat problematic, with a CTE of approximately 160 ppm/°C, and will likely require a nanoparticle composite strategy. However, this combination of material and lithographic properties make PMDA-TFMB a promising candidate for this application.