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Triethoxysilyl functionalized hyperbranched polsiloxysilanes at the focal (FT-HBPSs) and terminal (TT-HBPSs) positions were synthesized to investigate adsorption behavior onto a silicon wafer surface. The surface of the silicon wafer adsorbed with the HBPSs was characterized by X-ray photoelectron spectroscopy, atomic force microscopy (AFM), static and dynamic water contact angle measurements. The AFM images indicated the formation size of dot-like structures were approximately 200 nm. The presence of vinyl terminal groups of FT-HBPSs permitted conversion of the surface from a non-polar hydrocarbon to a polar hydroxylated or carboxylated structures. After the polarity was changed, the surface properties were also studied using the above surface analysis techniques. The dynamic contact angle measurement indicated that the silicon wafer surface modified by FT-HBPSs was more hydrophilic in water than TT-HBPS. This behavior can be explained by the difference of connecting points between HBPS and the silicon wafer surface.

Two new nitrile-containing diamine monomers, 4-[bis(4-aminophenyl)amino]benzonitrile and 4-[4-(1-cyanopropoxy)phenyl]2,6-bis(4-aminophenyl)pyridine were synthesized. The diamine monomers were reacted with various tetracarboxylic dianhydrides, followed by cyclodehydration (imidization) without isolation to produce a series of novel polyimides with pendant nitrile groups on the side chain. The polymers were obtained in quantitative yields with high molecular weight. Among them, polymers derived from ODPA and 6FDA showed good solubility, they could dissolve in polar solvents such as DMF, NMP, DMSO and even pyridine and m-cresol. These tough, transparent and flexible polyimide films had a tensile strength of 80–120 MPa, an elongation at break of 4–12% and a tensile modulus of 1.2–2.3 GPa. The polymers obtained exhibited high glass transition temperatures between 305 and 360 C. Moreover, they were fairly stable up to a temperature around or above 400 C and lost 10% weight in the range of 500–590 C and 470–580 C in nitrogen and air, respectively. Together the dielectric constants of the polyimides were measured to be 3.10–3.73 at 10 GHz. On the other hand, blank polyimides with no – CN groups were also prepared for comparison and the results revealed that the nitrile group affected the thermal property of polyimides as well as the electrical properties. Introduction of the –CN groups would increase the glass transition temperature and also the dielectric constant.

We describe the synthesis, characterization, and lithographic performance of positive-working chemically amplified photosensitive polybenzoxazoles (PSPBOs) composed of partially tert-butoxycarbonyl (t-BOC) protected hyperbranched poly(o-hydroxyamide)s (HB-tbocPHAs) and diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate (DIAS) as a photo-acid generator (PAG). The HB-tbocPHAs as precursors of PSPBOs were synthesized from hyperbranched poly(o-hydroxyamide)s (HBPHAs), which were prepared by self-polycondensation of an AB 2 type monomer. A series of HB-tbocPHAs having the t-BOC content of 8-100 mol % were successfully prepared by controlling the feed amount of di-tert-butyl dicarbonate (DTBDC). HB-tbocPHAs had adequate dissolution rate in tetramethylammonium hydroxide (TMAH) aqueous solution as well as excellent solubility in common organic solvents. HB-tbocPHA having 39 mol % t-BOC group showed the optimum dissolution rate in 2.38 wt% TMAH aqueous solution and good adhesion on a silicon wafer. The thermal deprotection of the t-BOC group and conversion to polybenzoxazole (PBO) of HB-tbocPHA in the presence of strong acid such as p-toluenesulfonic acid (p-TsOH) were investigated by using FT-IR, DSC, and TGA to examine the acid effect. Both the deprotection of t-BOC groups and the conversion to PBO were accelerated in the presence of p-TsOH. The photolithographic performance of the resist formulated with HB-tbocPHA and 20 wt % of DIAS was evaluated. The resist showed 115 mJ/cm 2 of sensitivity and 2.2 of contrast with 365 nm light when it was developed in 2.38 wt % TMAH aqueous solution at room temperature. The fine positive pattern was obtained at the 200 mJ/cm 2 of i-line exposure. The patterned film was successfully converted to polybenzoxazole without any distortion by thermal treatment at 300 °C for 1 h.

Hyperbranched polysiloxysilane (HBPS) terminated by the vinyl functional group was synthesized by the self polymerization of AB2 monomer, 1,5-divinyl-1,1,3,5,5-pentamethyltrisiloxane, in the presence of the platinum catalyst. The terminal vinyl group was converted to 2-hydroxyethyl by the reaction with 9-BBN as the hydroboration reagent. The terminal function was then modified to the 2-bromoisobutyryl group by the reaction of hydroxyl group with 2-bromoisobutyryl bromide. The obtained HBPS possessing the 2-bromoisobutyryl terminal group was immobilized on the silica surface by mixing the silica bead and HBPS in hexane. Block copolymer of HBPS and poly(N-isopropylacrylamide) (PIPAAm) was synthesized by the atom transfer radical polymerization (ATRP) using 2-bromoisobutyryl terminated HBPS as a macroinitiator. The molecular weight of the block copolymer was Mn=23,500 and Mw/Mn=1.31. Graft polymerization of N-isopropylacrylamide on the silica surface was carried out on the 2-bromoisobutyryl terminated HBPS immobilized silica bead using ATRP. The PIPAAm grafted silica bead was applied to the column packed material for temperature-responsive HPLC. Two kinds of steroids, hydrophilic and hydrophobic, were successfully separated by the HPLC system.