Flexible Ultrathin Chip-Film Patch for Electronic Component Integration and Encapsulation using Atomic Layer-Deposited Al2O3-TiO2 Nanolaminates.

Plasma-enhanced atomic layer deposition (PEALD) is utilized to improve the barrier properties of an organic chip-film patch (CFP) when it is used as an implant to prevent moisture and ions from migrating into the embedded electronic circuits. For this purpose, surface condition and material properties of eight modifications of Al2O3-TiO2 nanolaminates sequentially deposited on polyimide PI-2611 films are evaluated in detail. The effect of stress-induced warpage of the deposited Al2O3-TiO2 on the wafer level is calculated with the Stoney equation and reveals higher tensile stress values while increasing the thickness of Al2O3-TiO2 nanolaminates from 20 up to 80 nm. Contact angle measurement and atomic force microscopy are used to investigate the surface energy and wettability, as well as the surface morphology of polyimide-Al2O3-TiO2 interfaces. We show that plasma treatment of pristine polyimide leads to an enhanced adhesion force of the PEAL-deposited layer by a factor of 1.3. The water vapor transmission rate (WVTR) is determined by exposing the coated polyimide films to 85% humidity and 23 °C and yields down to 1.58 × 10-3 g(H2O)/(m2 d). The data obtained are compared with alternative coating processes using the polymers parylene-C and benzocyclobutene (BCB). The latter shows higher WVTR values of 1.2 × 10-1 and 1.7 × 10-1 g(H2O)/(m2 d) compared to the PEALD-PI-2611 systems, indicating lower barrier properties. Two Al2O3-TiO2 modifications with low WVTR values have been chosen for encapsulating the CFP substrates and exposing them in a long-time experiment to chemical and mechanical loads in a chamber filled with phosphate-buffered saline at 37 °C, pH 7.3, and a cyclically applied pressure of 160 mbar (∼120 mm Hg). The electrical leakage behavior of the CFP systems is measured and reveals reliable electrical long-term stability far beyond 11 months, highlighting the great potential of PEALD-encapsulated CFPs.

Head-to-Tail Regioregular Polythiazole Prepared via Kumada-Coupling Polycondensation.

Head-to-tail regioregular poly(4-alkylthiazoles) (C9-pTz, C13-pTz, alkyl = n-C9H19, n-C13H27) have been synthesized and spectroscopically and electrochemically characterized. The PTzs were obtained by transmetalation of 2-chloro-5-bromo-4-alkylthiazoles with iPrMgCl, followed by Kumada-coupling polycondensation. The polymers are largely insoluble in organic solvents but dissolve readily in the presence of, e.g., trifluoro acetic acid (TFA). Analyses of soluble trace fractions of the polymers gave number average molecular weights (Mn) of 1.9-2.4 kDa (C9-pTz, PDI ≈ 1.1-1.3) and 2.9-3.0 kDa (C13-pTz, PDI ≈ 1.1-1.2), as determined by gel permeation chromatography (GPC) relative to polystyrene standards, while the molecular weight of the bulk material is presumed to be considerably higher. Comparison of the 1H NMR spectra of the PTzs with a quaterthiazole model compound (4Tz) and head-to-head-tail-to-tail regioregular polybithiazole (PBTz) confirmed the head-tail structure and the high degree of regioregularity. The optical and electrochemical band gaps of C9-PTz were found to be similar to those of poly(3-hexylthiophene) (P3HT), while the frontier orbital levels are stabilized by 0.3-0.5 eV relative to those of the polythiophene. The synthesis of PTz via selective transmetalation of the precursor at the sterically hindered 5-position renders this synthesis a rare polycondensation of a reversed monomer. The implications for the polymerization mechanism are also discussed.