Direct Writing and Characterization of Three-Dimensional Conducting Polymer PEDOT Arrays

Direct writing is an effective and versatile technique for three-dimensional (3D) fabrication of conducting polymer (CP) structures. It is precisely localized and highly controllable, thus providing great opportunities for incorporating CPs into microelectronic array devices. Herein we demonstrate 3D writing and characterization of poly­(3,4-ethylenedioxythiophene)-polystyrenesulfonate (PEDOT:PSS) pillars in an array format, by using an in-house-constructed variant of scanning ion conductance microscopy (SICM). CP pillars with different aspect ratios were successfully fabricated by optimizing the writing parameters: pulling speed, pulling time, concentration of the polymer solution, and the micropipette tip diameter. Especially, super high aspect ratio pillars of around 7 μm in diameter and 5000 μm in height were fabricated, indicating a good capability of this direct writing technique. Additions of an organic solvent and a cross-linking agent contribute to a significantly enhanced water stability of the pillars, critical if the arrays were to be used in biologically relevant applications. Surface morphologies and structural analysis of CP pillars were characterized by scanning electron microscopy and Raman spectroscopy, respectively. Electrochemical properties of the individual pillars of different heights were examined by cyclic voltammetry using a double-barrel micropipette as an electrochemical cell. Exceptional mechanical properties of the pillars, such as high flexibility and robustness, were observed when bent by applying a force. The 3D pillar arrays are expected to provide versatile substrates for functionalized and integrated biological sensing and electrically addressable array devices

A Label-Free, Sensitive, Real-Time, Semiquantitative Electrochemical Measurement Method for DNA Polymerase Amplification (ePCR)

Oligonucleotide hybridization to a complementary sequence that is covalently attached to an electrochemically active conducting polymer (ECP) coating the working electrode of an electrochemical cell causes an increase in reaction impedance for the ferro-ferricyanide redox couple. We demonstrate the use of this effect to measure, in real time, the progress of DNA polymerase chain reaction (PCR) amplification of a minor component of a DNA extract. The forward primer is attached to the ECP. The solution contains other PCR components and the redox couple. Each cycle of amplification gives an easily measurable impedance increase. Target concentration can be estimated by cycle count to reach a threshold impedance. As proof of principle, we demonstrate an electrochemical real-time quantitative PCR (e-PCR) measurement in the total DNA extracted from chicken blood of an 844 base pair region of the mitochondrial Cytochrome c oxidase gene, present at ∼1 ppm of total DNA. We show that the detection and semiquantitation of as few as 2 copies/μL of target can be achieved within less than 10 PCR cycles

Molecularly Engineered Intrinsically Healable and Stretchable Conducting Polymers

Advances in stretchable electronics concern engineering of materials with strain-accommodating architectures and fabrication of nanocomposites by embedding a conductive component into an elastomer. The development of organic conductors that can intrinsically stretch and repair themselves after mechanical damage is only in the early stages yet opens unprecedented opportunities for stretchable electronics. Such functional materials would allow extended lifetimes of electronics as well as simpler processing methods for fabricating stretchable electronics. Herein, we present a unique molecular approach to intrinsically stretchable and healable conjugated polymers. The simple yet versatile synthetic procedure enables one to fine-tune the electrical and mechanical properties without disrupting the electronic properties of the conjugated polymer. The designed material is comprised of a hydrogen-bonding graft copolymer with a conjugated backbone. The morphological changes, which are affected by the composition of functional side chains, and the solvent quality of the casting solution play a crucial role in the synthesis of highly stretchable and room-temperature healable conductive electronic materials