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Polymers for all-organic field-effect transistors are under development to cope with the increasing demand for novel materials for organic electronics. Besides the semiconductor, the dielectric layer determines the efficiency of the final device. Poly(methyl methacrylate) (PMMA) is a frequently used dielectric. In this work, the chemical structure of this material was stepwise altered by incorporation of cross-linkable and/or self-organizing comonomers to improve the chemical stability and the dielectric properties. Different types of cross-linking methods were used to prevent dissolution, swelling or intermixing of the dielectric e.g. during formation processes of top electrodes or semiconducting layers. Self-organizing comonomers were expected to influence the dielectric/semiconductor interface, and moreover, to enhance the chemical resistance of the dielectric. Random copolymers were obtained by free radical and reversible addition-fragmentation chain transfer (RAFT) polymerization. With 6-[4-(4'-cyanophenyl)phenoxy]alkyl side chains having hexyl or octyl spacer, thermotropic liquid crystalline (LC) behavior and nanophase separation into smectic layers was observed, while copolymerization with methyl methacrylate induced molecular disorder. In addition to chemical, thermal and structural properties, electrical characteristics like breakdown field strength (EBD) and relative permittivity (k) were determined. The dielectric films were studied in metal-insulator-metal setups. EBD appeared to be strongly dependent on the type of electrode used and especially the ink formulation. Cross-linking of PMMA yielded an increase in EBD up to 4.0 MV/cm with Ag and 5.7 MV/cm with, Pedot: PSS electrodes because of the increased solvent resistance. The LC side chains reduce the ability for cross-linking resulting in decreased breakdown field strengths.

The N-type semiconducting polymer, P(NDI2OD-T2), with different molecular weights (MW=23, 72, and 250 kg/mol) was used for the fabrication of field-effect transistors (FETs) with different semiconductor layer thicknesses. FETs with semiconductor layer thicknesses from ∼15 to 50 nm exhibit similar electron mobilities (μ's) of 0.2-0.45 cm2 V(-1) s(-1). Reduction of the active film thickness led to decreased μ values; however, FETs with ∼2 and ∼5 nm thick P(NDI2OD-T2) films still exhibit substantial μ's of 0.01-0.02 and ∼10(-4) cm2 V(-1) s(-1), respectively. Interestingly, the lowest molecular weight sample (P-23, MW≈23 kg/mol, polydispersity index (PDI)=1.9) exhibited higher μ than the highest molecular weight sample (P-250, MW≈250 kg/mol, PDI=2.3) measured for thicker devices (15-50 nm). This is rather unusual behavior because typically charge carrier mobility increases with MW where improved grain-to-grain connectivity usually enhances transport events. We attribute this result to the high crystallinity of the lowest MW sample, as confirmed by differential scanning calorimetry and X-ray diffraction studies, which may (over)compensate for other effects.

Sequential copolymerizations of trimethylene carbonate (TMC) and l-lactide (LLA) were performed with 2,2-dibutyl-2-stanna-1,3-oxepane as a bifunctional cyclic initiator. The block lengths were varied via the monomer/initiator and via the TMC/l-lactide ratio. The cyclic triblock copolymers were transformed in situ into multiblock copolymers by ring-opening polycondensation with sebacoyl chloride. The chemical compositions of the block copolymers were determined from (1)H NMR spectra. The formation of multiblock structures and the absence of transesterification were proven by (13)C NMR spectroscopy. Differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS), and dynamic mechanical analysis (DMA) measurements confirmed the existence of a microphase-separated structure in the multiblock copolymers consisting of a crystalline phase of poly(LLA) blocks and an amorphous phase formed by the poly(TMC) blocks. Stress-strain measurements showed the elastomeric character of these biodegradable multiblock copolymers, particularly in copolymers having epsilon-caprolactone as comonomer in the poly(TMC) blocks.