Advances in Efficient Polymerization of Solid-State Trithiophenes for Organic Thermoelectric Thin-Film

Abstract

The polymerization of solid-state small organic molecules generally involving no less three units has been demonstrated to be an important prospect in the field of organic electrons. Presently, owing to the chemical coupling reactions, the polymerization for solid-state small molecules usually involves the complex operations and results in powder polymers and a poor-quality thin-film by spin coating due to their insoluble property in common solvents. The conventional vapor-phase polymerization (VPP) is a powerful technology and has been widely accepted for a high-quality polymer film. However, the VPP is generally used for a limited small organic molecules, but does not apply to a solid-state organic molecules due to the difficulty of vaporization. Herein, we proposed an upgrade vapor phase polymerization strategy, spin-spray coating polymerization method, to overcome the limitation of traditional VPP by spraying of solid-state trithiophenes as precursors in a common low-boiling point organic solvent for a homogeneous conjugated polymer thin-film. The as-fabricated conjugated polymer films show the uniform morphology with the fast and easy polymerization and acceptable thermoelectric performance compared to the traditional chemical and electrochemical oxidation in solution. This spin-spray coating polymerization technique has also been extended to the derivatives of trithiophenes with different alkyl side chains in thiophene, demonstrating the effective strategy for the development of an uniform polymer thin-film with relatively complex structure.

Optimizing the Optoelectronic Properties of Face‐On Oriented Poly(3,4‐Ethylenedioxythiophene) via Water‐Assisted Oxidative Chemical Vapor Deposition

“…PEDOT is often spin‐coated with polystyrene sulfonate (PSS) to form PEDOT:PSS, [ 8,9 ] but PEDOT thin films can also be fabricated by electropolymerization, [ 10,11 ] in situ chemical polymerization, [ 12–15 ] vapor phase polymerization (VPP), [ 16–19 ] and oxidative chemical vapor deposition (oCVD). [ 20–26 ] For PEDOT, the highest value of σ to date, 8797 ± 1178 S cm −1 , was reported by Cho et al.…”

Oxidative MLD of Conductive PEDOT Thin Films with EDOT and ReCl5 as Precursors

“…Vapor-phase polymerization (VPP) ,− is based on a similar concept to ICP, but instead of mixing EDOT to the oxidant solution, oxidants adsorbed on a substrate surface are exposed to EDOT vapors . A recent approach to the PEDOT film deposition is chemical vapor deposition (CVD) − using EDOT and FeCl 3 , , Br 2 , MoCl 5 , SbCl 5 , or VOCl 3 as an oxidant.…”

Thiophene-Based Trimers and Their Bioapplications: An Overview

“…Kumada reaction was also applied to the synthesis of other unsubstituted EDOT-based trimers, such as thiophene-EDOT-thiophene [ 60 , 61 ] or EDOT-Thiophene-EDOT [ 62 , 63 ]. In alternative, Suzuki [ 64 , 65 , 66 ] and Stille [ 67 , 68 , 69 , 70 ] coupling reactions offer valuable routes for the synthesis of EDOT-based trimers. EDOT organoboron and organotin compounds can be easily synthesized and further coupled with aryl-halide to complete the synthesis of EDOT-based trimers.…”