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Energy‐harvesting technologies offer a sustainable, maintenance‐free alternative to conventional energy‐storage solutions in distributed low‐power applications. Flexible thermoelectric generators (TEGs) can generate electric power from a temperature gradient, even on complex surfaces. Organic materials are ideal candidates for flexible TEGs due to their good solution‐processability, natural abundance, low weight, and flexibility. Electronic and thermoelectric properties of organic materials have steadily progressed, while device architectures leveraging their advantages are largely missing. Here, a design and fabrication method are proposed for producing fully screen‐printed, flexible monolithic organic TEGs scalable up to m2, compatible with any screen‐printable ink. This approach is validated, along with its scalability, by printing TEGs composed of two different active inks, in three configurations, with up to 800 thermoelements, with performances well matching simulations based on materials parameters. It is demonstrated that by using an additive‐free graphene ink, a remarkable power density of 15 nW cm−2 at ΔT = 29.5 K can be achieved, with an estimated weight‐normalized power output of 1 µW g−1, highlighting a strong potential in portability. Owing to such power density, only limited areas are required to generate microwatts, sufficient for operating low‐power electronic devices such as sensors, and wearables. [ABSTRACT FROM AUTHOR]

Functionally graded materials (FGMs) are widely explored in the context of inorganic thermoelectrics, but not yet in organic thermoelectrics. Here, the impact of doping gradients on the thermoelectric properties of a chemically doped conjugated polymer is studied. The in‐plane drift of counterions in moderate electric fields is used to create lateral doping gradients in films composed of a polythiophene with oligoether side chains, doped with 2,3,5,6‐tetrafluoro‐tetracyanoquinodimethane (F4TCNQ). Raman microscopy reveals that a bias voltage of as little as 5 V across a 50 µm wide channel is sufficient to trigger counterion drift, resulting in doping gradients. The effective electrical conductivity of the graded channel decreases with bias voltage, while an overall increase in Seebeck coefficient is observed, yielding an up to eight‐fold enhancement in power factor. Kinetic Monte Carlo simulations of graded films explain the increase in power factor in terms of a roll‐off of the Seebeck coefficient at high electrical conductivities in combination with a mobility decay due to increased Coulomb scattering at high dopant concentrations. Therefore, the FGM concept is found to be a way to improve the thermoelectric performance of not yet optimally doped organic semiconductors, which may ease the screening of new materials as well as the fabrication of devices. [ABSTRACT FROM AUTHOR]

Molecular doping is a key strategy to enhance the electrical conductivity of organic semiconductors. Typically, the electrical conductivity shows a maximum value upon increased doping, after which the conductivity decreases. This decrease in conductivity is commonly attributed to unfavorable changes in the morphology. However, in recent simulation work, has shown, that the conductivity-at high doping-is instead limited by electron-electron repulsion rather than by morphology, at least for some material combinations. Based on the simulations, this limitation is expected to show up in the dependence of the Seebeck coefficient versus carrier density: the Seebeck coefficient will follow Heike's formula if carrier-carrier repulsion limits the conductivity. Here, the electrical conductivity and Seebeck coefficient are measured as a function of doping for a series of n-type organic semiconductors. Additionally, the resulting carrier density is measured using metal-insulator-semiconductor diodes, which link dopant loading and the number of charge carriers. At high carrier densities, the Seebeck coefficient indeed follows Heike's formula, confirming that the conductivity is limited by carrier-carrier repulsion rather than by morphological effects. This study shows that current models of hopping transport in organic semiconductors may be incomplete. As a result, this study offers novel insights in the design of organic semiconductors., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)