Additive Manufacturing Based on Electrochemistry

Abstract

A fabrication method combining 3D printing and multi-material electrodeposition is introduced in this thesis. The method combines electrochemical and three-dimensional control of electrode positions to culminate in a new process for 2D patterning and the 3D printing of metals, semiconductors, as well as polymers into complex shapes with feature sizes as small as 10 um. The method specifically allows access to patterned or printed, previously difficult-to-process electrically conductive pi-conjugated polymers. The technique uses electrodes in a solution of an electrodepositable material to perform electrochemical printing, a process that can be controlled by varying the inter-electrode gap, the applied potential or current, the electrode geometry and dimension, the electrodeposition solution (ink), movement direction, and movement speed. The first chapter introduces the concepts of electrodeposition and localized electrodeposition and applies them to electrochemical printing. It also explores the influence of the different parameters which affect the printing process and introduces the types of materials that can be printed using this method. In Chapter 2, electrochemical printing is shown to have a unique combination of speed and resolution, multi-material printing, and morphology control, culminating in multi-material device fabrication. In Chapter 3, the first steps are made in monitoring the electrochemical reactions and localized deposition processes in-situ by combining electrochemical analytical methods such as cyclic voltammetry and chronoamperometry with electrochemical quartz crystal microgravimetry. Using poly(3,4-ethylenedioxythiophene) (PEDOT) as a model system, we study the effects that the composition of the supporting electrolyte and solvent used, de-oxygenation and monomer concentration had on the polymerization yield. In Chapter 4, a brand-new approach involving the ferrocene-mediated cationic electrochemical printing of bisphenol A diglycidyl ether and tris[4-hydroxyphenyl] methane triglycidyl ether) based on electrochemically controlled ring-opening polymerization is demonstrated. The development of this novel fabrication method combining 3D printing and multi-material electrodeposition opens new pathways for advanced material design and manufacturing. By enabling precise, controlled deposition of metals, semiconductors, and conductive polymers in complex 2D and 3D architectures, this technique can significantly enhance applications in fields such as flexible electronics, biosensors, and energy storage devices. The ability to pattern previously hard-to-process conductive polymers also presents opportunities for innovations in organic electronics and optoelectronic devices. The versatility and scalability of this method position it as a promising platform for future research and development in multi-material printing and electrochemical manufacturing, potentially unlocking the production of functional materials and devices. Show more