Direct printing of functional 3D objects using polymerization-induced phase separation.

3D printing has enabled materials, geometries and functional properties to be combined in unique ways otherwise unattainable via traditional manufacturing techniques, yet its adoption as a mainstream manufacturing platform for functional objects is hindered by the physical challenges in printing multiple materials. Vat polymerization offers a polymer chemistry-based approach to generating smart objects, in which phase separation is used to control the spatial positioning of materials and thus at once, achieve desirable morphological and functional properties of final 3D printed objects. This study demonstrates how the spatial distribution of different material phases can be modulated by controlling the kinetics of gelation, cross-linking density and material diffusivity through the judicious selection of photoresin components. A continuum of morphologies, ranging from functional coatings, gradients and composites are generated, enabling the fabrication of 3D piezoresistive sensors, 5G antennas and antimicrobial objects and thus illustrating a promising way forward in the integration of dissimilar materials in 3D printing of smart or functional parts.

Formulation of Screen-Printable Cu Molecular Ink for Conductive/Flexible/Solderable Cu Traces.

Screen printing is the most common method used for the production of printed electronics. Formulating copper (Cu) inks that yield conductive fine features with oxidation and mechanical robustness on low-temperature substrates will open up opportunities to fabricate cost-effective devices. We have formulated a screen-printable Cu metal-organic decomposition (MOD) ink comprising Cu formate coordinated to 3-(diethylamino)-1,2-propanediol, a fractional amount of Cu nanoparticles (CuNPs), and a binder. This simple formulation enables ∼70-550 µm trace widths with excellent electrical [∼8-15 mΩ/□/mil or 20-38 µΩ·cm] and mechanical properties with submicron-thick traces obtained by intense pulse light (IPL) sintering on Kapton and poly(ethylene terephthalate) (PET) substrates. These traces are mechanically robust to flexing and creasing where less than 10% change in resistance is observed on Kapton and ∼20% change is observed on PET. Solderable Cu traces were obtained only with the combination of the Cu MOD precursor, CuNP, and polymer binder. Both thermally and IPL sintered traces showed shelf stability (<10% change in resistance) of over a month in ambient conditions and 10-70% relative humidity, suitable for day-to-day fabrication. To demonstrate utility, light-emitting diodes (LEDs) were directly soldered to IPL sintered Cu traces in a reflow oven without the need for a precious metal interlayer. The LEDs were functional not only during bending and creasing of the Cu traces but even after 180 min at 140 °C in ambient air without losing illumination intensity. High definition television antennas printed on Kapton and PET were found to perform well in the ultrahigh frequency region. Lastly, single-walled carbon nanotube-based thin-film transistors on a silicon wafer were fabricated with a screen-printed Cu source and drain electrodes, which performed comparably to silver electrodes with mobility values of 12-15 cm2 V-1 s-1 and current on/off ratios of ∼105 and as effective ammonia sensors providing parts per billion-level detection.

The role of amine ligands in governing film morphology and electrical properties of copper films derived from copper formate-based molecular inks.

Copper formate complexes with various primary amines, secondary amines and pyridines were prepared, and their decomposition into conductive films was characterized. A comparison of the various complexes reveals that the temperature of thermolysis depends on the number of hydrogen bonds that can be formed between the amine and formate ligands. The particle size resulting from sintering of the copper complexes is shown to depend on the fraction of amine ligand released during the thermolysis reaction. The particle size in turn is shown to govern the electrical properties of the copper films. Correlations between the properties of the amines, such as boiling point and coordination strength, with the morphology and electrical performance of the copper films were established and provide a basis for the molecular design of copper formate molecular inks.

Versatile Molecular Silver Ink Platform for Printed Flexible Electronics.

A silver molecular ink platform formulated for screen, inkjet, and aerosol jet printing is presented. A simple formulation comprising silver neodecanoate, ethyl cellulose, and solvent provides improved performance versus that of established inks, yet with improved economics. Thin, screen-printed traces with exceptional electrical (<10 mΩ/□/mil or 12 µΩ·cm) and mechanical properties are achieved following thermal or photonic sintering, the latter having never been demonstrated for silver-salt-based inks. Low surface roughness, submicron thicknesses, and line widths as narrow as 41 µm outperform commercial ink benchmarks based on flakes or nanoparticles. These traces are mechanically robust to flexing and creasing (less than 10% change in resistance) and bind strongly to epoxy-based adhesives. Thin traces are remarkably conformal, enabling fully printed metal-insulator-metal band-pass filters. The versatility of the molecular ink platform enables an aerosol jet-compatible ink that yields conductive features on glass with 2× bulk resistivity and strong adhesion to various plastic substrates. An inkjet formulation is also used to print top source/drain contacts and demonstrate printed high-mobility thin film transistors (TFTs) based on semiconducting single-walled carbon nanotubes. TFTs with mobility values of ∼25 cm2 V-1 s-1 and current on/off ratios >104 were obtained, performance similar to that of evaporated metal contacts in analogous devices.

Porous conducting polymer/heteropolyoxometalate hybrid material for electrochemical supercapacitor applications.

A porous conducting polymer/heteropolyoxometalate hybrid material that displays high specific capacitance and low ionic resistance has been prepared for electrochemical supercapacitor applications. Polypyrrole/phosphomolybdate composite films were chemically synthesized in tetrahydrofuran in the presence of sodium sulfate, which acts as a porogen. While the phosphomolydic acid could be removed from the film upon rinsing with pure tetrahydrofuran or acetone, rinsing with water or methanol resulted in retention of the heteropolyoxometalate at a level high enough to easily observe its electrochemistry. The retained phosphomolybdate exhibits fast and reversible redox behavior, adding a significant amount of pseudocapacitance to the polymer. Porous films were obtained by leaching out the sodium sulfate porogen from the films using water. The morphology obtained using this method is altered by varying the monomer-to-porogen ratio. Increasing the porosity increases the rate at which the hybrid material can be charged/discharged (i.e., oxidized/reduced) by increasing the ionic conductivity and in turn lowering the resistor-capacitor time constant of the material. The ability to tune the porosity of the material allows the optimization of performance characteristics for use in supercapacitor applications. Impedance measurements indicate that the ionic conductivity of these porous structures can be increased more than an order of magnitude over that observed for standard conducting polymer films and that the hybrid material displays peak specific capacitance of around 700 F/g as well as excellent reversibility and cyclability.

A novel layer-by-layer approach for the fabrication of conducting polymer/RNA multilayer films for controlled release.

Poly(anilineboronic acid) (PABA)/ribonucleic acid (RNA) multilayer films were prepared under neutral condition using a layer-by-layer deposition of PABA and RNA. RNA was used both as a polyelectrolyte for multilayer formation as well as dopant for PABA. Photoelastic modulated infrared reflection absorption spectroscopy measurements suggest that PABA interacts covalently with RNA through the formation of a boronate ester, a boron-nitrogen dative bond, as well as electrostatic interactions of anionic phosphates with cationic amines. The deposition procedure was monitored with UV-vis absorption spectroscopy, showing a linear dependence of absorbance with the number of PABA/RNA bilayers deposited. The multilayer films were further characterized using X-ray photoelectron spectroscopy and ellipsometry, which yielded a PABA/RNA bilayer thickness of approximately 10 nm. The PABA/RNA multilayer films are redox-active at neutral pH, consistent with the formation of a self-doped polymer. Electrochemical control of PABA under these conditions allows potential-induced controlled release of RNA from a multilayer at neutral pH, suggesting that this may serve as a novel method for controlled release of RNA under physiological conditions.

Substitution and condensation reactions with poly(anilineboronic acid): reactivity and characterization of thin films.

Poly(anilineboronic acid) thin films are treated under various conditions to achieve substitution or condensation reactions involving the boronic acid moiety. These reactions are studied with polarization modulated infrared reflection absorption spectroscopy, cyclic voltammetry, and UV-vis spectroscopy. The results suggest the single-step formation of substituted polyanilines, such as poly(hydroxyaniline), halogenated polyanilines, and mercury chloride-substituted polyaniline. A condensation reaction of poly(anilineboronic acid) with cis-diol compounds in aqueous solution, as well as with phenylenebisboronic acid and salycilamide in THF, indicates the formation of boronic esters. The latter reactions appear to be a good entry point for the formation of complex or supramolecular polymer structures.

A switchable self-doped polyaniline: interconversion between self-doped and non-self-doped forms.

A novel strategy for the synthesis of a substituted polyaniline that can be switched between a self-doped and non-self-doped state is presented. The approach uses the complexation between boronic acid-substituted aniline, a diol (d-fructose), and fluoride to generate an anionic monomer. Under these conditions, chemical polymerization results in a self-doped, water-soluble, conducting polyaniline under neutral aqueous conditions. The self-doped polymer can be simply and reversibly converted to an insoluble non-self-doped form by reducing the concentration of fluoride. Characteristics of the polymerization reaction and the resulting polymer are discussed.

Saccharide imprinting of poly(aniline boronic acid) in the presence of fluoride.

A new approach for the electrosynthesis of saccharide-imprinted poly(aniline boronic acid) is described. The method involves the formation of a saccharide-aminophenylboronic acid complex in the presence of fluoride to allow the electropolymerization of a self-doped, molecularly imprinted polyaniline. The formation of the anionic monomer complex enables electrochemical polymerization at near neutral pH (5-7) ensuring the incorporation of saccharide in the resulting, self-doped polymer. In this work, films were imprinted with D-fructose where saccharide-aminophenylboronic acid complexation occurred in the presence of one equivalent of fluoride. The selectivity toward D-fructose relative to D-glucose showed an increase of over 25% as a result of imprinting. In addition to the enhanced selectivity, to the best of our knowledge this is the first example of the electropolymerization of a self-doped polyaniline homopolymer under neutral pH conditions.

Enantioselective uptake of amino acids using an electromodulated column packed with carbon fibres modified with overoxidised polypyrrole.

A column packed with carbon fibres modified with overoxidized polypyrrole was utilised for the enantioselective uptake of glutamic acid. The polypyrrole prepared with L-glutamate as a dopant was electrochemically overoxidised to create a complementary cavity for the dopant. The target amino acid enantiomers were taken up and released by applying potential to the carbon fibre stationary phase. The uptake performance of an overoxidised polypyrrole modified carbon fibre electrode was investigated by optimising various important overoxidation parameters such as an overoxidation medium and applied potential. Under optimised conditions of overoxidation and with a column wash between the consecutive measurements, the reproducible uptake of L-glutamic acid was almost six times higher than that of D-glutamic acid. Further, in a comparison, the recognition ability of overoxidized polypyrrole with a pseudo-template cavity was examined.

Characterization of overoxidized polypyrrole colloids imprinted with L-lactate and their application to enantioseparation of amino acids.

Overoxidized polypyrrole colloids imprinted with L-lactate were prepared to evaluate the performance of the overoxidation pseudo-template technique developed by the authors. A polypyrrole colloid that had been prepared from a mixture of monomer (pyrrole), dopant (L-lactate), steric stabilizer (poly(vinylpyrrolidone)) and oxidizing agent (peroxodisulfate) was electrochemically overoxidized at +1.5 V vs Ag/AgCl to create a complementary cavity for recognition of the molecules, which were structurally similar to dopant, through dedoping. As a target molecule for enantioselective uptake into the overoxidized colloid, we selected alanine, which is structurally different from the template (lactate) only in one side chain (alanine, -NH2; lactic acid, -OH). The overoxidized polypyrrole colloid showed higher affinity for L-alanine than for D-alanine, and an uptake ratio (L/D) of as high as 11 +/- 4 was observed under optimum conditions. Uptake reached equilibrium in 10 min, thanks to the high surface area and short diffusion length in the colloidal particle. Further, to confirm the complementarity of the cavity, the effect of side chain size on uptake of several alpha-amino acids was examined to indicate that the uptake amount decreased with increasing molecular volume of the L-amino acids.

Highly selective molecularly imprinted overoxidized polypyrrole colloids: one-step preparation technique.

A convenient "one step" preparation process of molecularly imprinted overoxidized-polypyrrole (oPPy) colloids by chemical polymerization and their high uptake ability and enantioselectivity are described. Since an oxidizing agent gives a different standard redox potential and rate of polymerization, the property of the resulting oPPy colloid can be controlled by the kind and concentration of the oxidizing agent. At higher concentrations of (NH4)2S2O8 (0.3 M), the overoxidation of PPy colloid automatically occurred. The extraction of L-lactate as a dopant has created a shape-complementary cavity on the surface of the oPPy colloid through overoxidation following polymerization. The oPPy colloid exhibited an excellent selectivity not only on the alanine enantiomer but also on the difference in the side-chain size of amino acids. The uptake of oPPy colloid towards L-alanine over D-alanine was 11.3 micromol/g-colloid against 3.6 micromol/g. The molecularly imprinted cavity can also recognize the existences of the OH or CH3 substituents.

Pulsed amperometric detection of underivatized amino acids using polypyrrole modified copper electrode in acidic solution.

The successful pulsed amperometric detection of underivatized amino acids have been carried out in an acidic media on a polypyrrole (PPy) modified Cu electrode. The formation of PPy film doped with glutamate (glu) on a Cu electrode surface changes the mechanism of Cu dissolution. After application of multistep potential waveform, the PPy film was glu free due to the electro-reduction and overoxidation. High anodic potential polarization treatment yielded partially overoxidized PPy film as long as the Cu surface dissolution and amino acid permeation through the film was well controlled. This overoxidized PPy film acted as a charge and size exclusion barrier in order to improve the selectivity and stability of a Cu electrode. Various process parameters such as film modification time, detection and cleaning potential and pH of solution have been optimized to maximize the beneficial electrocatalytic properties of the electrode surface. At an optimized condition, detection limits for positively charged histidine and arginine are 19 and 22 pg respectively, whereas the neutral amino acids detected in amounts of 0.9-2.3 ng. Furthermore, the PPy coated Cu electrode response was long lived, stable and reproducible.