Liangqi Ouyang

Poly[3,4-ethylene dioxythiophene (EDOT)- co -1,3,5-tri[2-(3,4-ethylene dioxythienyl)]-benzene (EPh)] copolymers (PEDOT- co -EPh): optical, electrochemical and mechanical properties

PEDOT-co-EPh copolymers with systematic variations in composition were prepared by electrochemical polymerization from mixed monomer solutions in acetonitrile. The EPh monomer is a trifunctional crosslinking agent with three EDOTs around a central benzene ring. With increasing EPh content, the color of the copolymers changed from blue to yellow to red due to decreased absorption in the near infrared (IR) spectrum and increased absorption in the visible spectrum. The surface morphology changed from rough and nanofibrillar to more smooth with rounded bumps. The electrical transport properties dramatically decreased with increasing EPh content, resulting in coatings that either substantially lowered the impedance of the electrode (at the lowest EPh content), leave the impedance nearly unchanged (near 1% EPh), or significantly increase the impedance (at 1% and above). The mechanical properties of the films were substantially improved with EPh content, with the 0.5% EPh films showing an estimated 5x improvement in modulus measured by AFM nanoindentation. The PEDOT-co-EPh copolymer films were all shown to be non-cytotoxic toward and promote the neurite outgrowth of PC12 cells. Given these results, we expect that the films of most interest for neural interface applications will be those with improved mechanical properties that maintain the improved charge transport performance (with 1% EPh and below).

Significant enhancement of PEDOT thin film adhesion to inorganic solid substrates with EDOT-acid.

With its high conductivity, tunable surface morphology, relatively soft mechanical response, high chemical stability, and excellent biocompatibility, poly(3,4-ethylenedioxythiophene) (PEDOT) has become a promising coating material for a variety of electronic biomedical devices. However, the relatively poor adhesion of PEDOT to inorganic metallic and semiconducting substrates still poses challenges for long-term applications. Here, we report that 2,3-dihydrothieno(3,4-b)(1,4)dioxine-2-carboxylic acid (EDOT-acid) significantly improves the adhesion between PEDOT thin films and inorganic solid electrodes. EDOT-acid molecules were chemically bonded onto activated oxide substrates via the chemisorption of the carboxylic groups. PEDOT was then polymerized onto the EDOT-acid modified substrates, forming covalently bonded coatings. The adsorption of EDOT-acid onto the electrode surfaces was characterized by cyclic voltammetry (CV), contact angle measurements, atomic force microscopy, and X-ray photoelectron spectroscopy. The electrical properties of the subsequently coated PEDOT films were studied by electrochemical impedance spectroscopy and CV. An aggressive ultrasonication test confirmed the significantly improved adhesion and mechanical stability of the PEDOT films on electrodes with EDOT-acid treatment over those without treatment.

Enhanced PEDOT adhesion on solid substrates with electrografted P(EDOT-NH2)

Electrografted films of amine-functionalized thiophenes significantly improve coating adhesion and maintain charge transport. Conjugated polymers, such as poly(3,4-ethylene dioxythiophene) (PEDOT), have emerged as promising materials for interfacing biomedical devices with tissue because of their relatively soft mechanical properties, versatile organic chemistry, and inherent ability to conduct both ions and electrons. However, their limited adhesion to substrates is a concern for in vivo applications. We report an electrografting method to create covalently bonded PEDOT on solid substrates. An amine-functionalized EDOT derivative (2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanamine (EDOT-NH2), was synthesized and then electrografted onto conducting substrates including platinum, iridium, and indium tin oxide. The electrografting process was performed under slightly basic conditions with an overpotential of ~2 to 3 V. A nonconjugated, cross-linked, and well-adherent P(EDOT-NH2)–based polymer coating was obtained. We found that the P(EDOT-NH2) polymer coating did not block the charge transport through the interface. Subsequent PEDOT electrochemical deposition onto P(EDOT-NH2)–modified electrodes showed comparable electroactivity to pristine PEDOT coating. With P(EDOT-NH2) as an anchoring layer, PEDOT coating showed greatly enhanced adhesion. The modified coating could withstand extensive ultrasonication (1 hour) without significant cracking or delamination, whereas PEDOT typically delaminated after seconds of sonication. Therefore, this is an effective means to selectively modify microelectrodes with highly adherent and highly conductive polymer coatings as direct neural interfaces.

In vivo polymerization of poly(3,4-ethylenedioxythiophene) (PEDOT) in rodent cerebral cortex

Maintaining a reliable neural interface is a well-known challenge with implanted neural prostheses. Here we evaluate a method of forming an integrated neural interface through polymerization of PEDOT in vivo. Polymerization resulted in lower impedance and improved recording quality of local field potentials on implanted electrodes in the rat cerebral cortex. Histological analysis by optical microscopy confirmed successful integration of the PEDOT within tissue surrounding implanted electrodes. This technique offers a unique neural interfacing approach with potential to improve the long-term functionality of neural prostheses.

Direct local polymerization of poly(3,4-ethylenedioxythiophene) in rat cortex.

Glial scar encapsulation is thought to be one of the major reasons for the failure of chronic brain-machine interfaces. Many strategies, including modification of the probe surface chemistry, delivery of anti-inflammatory drugs, and changes of probe geometry, have been employed to reduce glial scar formation. We have proposed that a possible means to establish long-term, reliable communication across the scar is the in situ polymerization of conjugated polymers such as PEDOT in neural tissue. Previously, we exposed entire brain slices to the EDOT monomer. Here, we demonstrate that PEDOT can be polymerized by the direct delivery of EDOT monomer to the reaction site. The monomer was delivered into rat cortex via microcannula and simultaneously electrochemically polymerized within the tissue using a microwire electrode. We found that the resulting PEDOT polymer cloud grew out from the working electrode tip and extended far out into the brain tissue, spanning distances more than 1mm. We also examined the morphology of resulting polymer cloud by optical microscopy.

Stiffness, strength and adhesion characterization of electrochemically deposited conjugated polymer films.

UNLABELLED Conjugated polymers such as poly(3,4-ethylenedioxythiphene) (PEDOT) are of interest for a variety of applications including interfaces between electronic biomedical devices and living tissue. The mechanical properties, strength, and adhesion of these materials to solid substrates are all vital for long-term applications. We have been developing methods to quantify the mechanical properties of conjugated polymer thin films. In this paper, the stiffness, strength and the interfacial shear strength (adhesion) of electrochemically deposited PEDOT and PEDOT-co-1,3,5-tri[2-(3,4-ethylene dioxythienyl)]-benzene (EPh) were studied. The estimated Youngs modulus of the PEDOT films was 2.6±1.4GPa, and the strain to failure was around 2%. The tensile strength was measured to be 56±27MPa. The effective interfacial shear strength was estimated with a shear-lag model by measuring the crack spacing as a function of film thickness. For PEDOT on gold/palladium-coated hydrocarbon film substrates an interfacial shear strength of 0.7±0.3MPa was determined. The addition of 5mole% of a tri-functional EDOT crosslinker (EPh) increased the tensile strength of the films to 283±67MPa, while the strain to failure remained about the same (2%). The effective interfacial shear strength was increased to 2.4±0.6MPa. STATEMENT OF SIGNIFICANCE This paper describes methods for estimating the ultimate mechanical properties of electrochemically deposited conjugated polymer (here PEDOT and PEDOT copolymers) films. Of particular interest and novelty is our implementation of a cracking test to quantify the shear strength of the PEDOT thin films on these solid substrates. There is considerable interest in these materials as interfaces between biomedical devices and living tissue, however potential mechanisms and modes of failure are areas of continuing concern, and establishing methods to quantify the strengths of these interfaces are therefore of particular current interest. We are confident that these results will be useful to the broader biological materials community and are worthy of broader dissemination.

In Situ Electrochemical Deposition of Poly(3,4-ethylenedioxythiophene) (PEDOT)

Conjugated polymers are widely used in organic solar cells, chemical sensors and biomedical devices because of their relatively high conductivity and soft mechanical properties [1,2,3]. Electrochemical deposition has long been an important method of fabricating conjugated polymer thin films for various applications. The morphology of the films, and the corresponding performance of the devices is particularly sensitive to the detailed fabrication conditions. Previous efforts have investigated the nucleation and growth mechanisms of electropolymerized conjugated polymers, however the results are usually obtained from in-direct and lower resolution methods like UV-vis and AFM [4,5]. More detailed information with ultra-high resolution is still needed. Electrochemical liquid electron microscopy makes it possible to analyze this initial nucleation and growth process in direct imaging method in a TEM with nanometer scale resolution. This method has proven effective for the analysis of electrochemical deposition mechanisms in copper and lead [6,7]. No previous studies have examined the in situ TEM electrochemical deposition of conjugated polymers, mostly probably due to the fact that polymers are highly electron beam sensitive. This high sensitivity makes the in situ TEM imaging of conjugated polymer electrodeposition much more experimentally difficult than for inorganic materials.