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- Kiefer, David, 1989, et al.
(författare)
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Double doping of conjugated polymers with monomer molecular dopants
- 2019
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Ingår i: Nature Materials. - : Springer Science and Business Media LLC. - 1476-4660 .- 1476-1122. ; 18:2, s. 149-155
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Tidskriftsartikel (refereegranskat)abstract
- Molecular doping is a crucial tool for controlling the charge-carrier concentration in organic semiconductors. Each dopant molecule is commonly thought to give rise to only one polaron, leading to a maximum of one donor:acceptor charge-transfer complex and hence an ionization efficiency of 100%. However, this theoretical limit is rarely achieved because of incomplete charge transfer and the presence of unreacted dopant. Here, we establish that common p-dopants can in fact accept two electrons per molecule from conjugated polymers with a low ionization energy. Each dopant molecule participates in two charge-transfer events, leading to the formation of dopant dianions and an ionization efficiency of up to 200%. Furthermore, we show that the resulting integer charge-transfer complex can dissociate with an efficiency of up to 170%. The concept of double doping introduced here may allow the dopant fraction required to optimize charge conduction to be halved.
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| 2. |
- Beretta, Davide, et al.
(författare)
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Thermoelectrics: From history, a window to the future
- 2019
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Ingår i: Materials Science and Engineering: R: Reports. - : Elsevier BV. - 0927-796X. ; 138
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Forskningsöversikt (refereegranskat)abstract
- Thermoelectricity offers a sustainable path to recover and convert waste heat into readily available electric energy, and has been studied for more than two centuries. From the controversy between Galvani and Volta on the Animal Electricity, dating back to the end of the XVIII century and anticipating Seebeck's observations, the understanding of the physical mechanisms evolved along with the development of the technology. In the XIX century Ørsted clarified some of the earliest observations of the thermoelectric phenomenon and proposed the first thermoelectric pile, while it was only after the studies on thermodynamics by Thomson, and Rayleigh's suggestion to exploit the Seebeck effect for power generation, that a diverse set of thermoelectric generators was developed. From such pioneering endeavors, technology evolved from massive, and sometimes unreliable, thermopiles to very reliable devices for sophisticated niche applications in the XX century, when Radioisotope Thermoelectric Generators for space missions and nuclear batteries for cardiac pacemakers were introduced. While some of the materials adopted to realize the first thermoelectric generators are still investigated nowadays, novel concepts and improved understanding of materials growth, processing, and characterization developed during the last 30 years have provided new avenues for the enhancement of the thermoelectric conversion efficiency, for example through nanostructuration, and favored the development of new classes of thermoelectric materials. With increasing demand for sustainable energy conversion technologies, the latter aspect has become crucial for developing thermoelectrics based on abundant and non-toxic materials, which can be processed at economically viable scales, tailored for different ranges of temperature. This includes high temperature applications where a substantial amount of waste energy can be retrieved, as well as room temperature applications where small and local temperature differences offer the possibility of energy scavenging, as in micro harvesters meant for distributed electronics such as sensor networks. While large scale applications have yet to make it to the market, the richness of available and emerging thermoelectric technologies presents a scenario where thermoelectrics is poised to contribute to a future of sustainable future energy harvesting and management. This work reviews the broad field of thermoelectrics. Progress in thermoelectrics and milestones that led to the current state-of-the-art are presented by adopting an historical footprint. The review begins with an historical excursus on the major steps in the history of thermoelectrics, from the very early discovery to present technology. A panel on the theory of thermoelectric transport in the solid state reviews the transport theory in complex crystal structures and nanostructured materials. Then, the most promising thermoelectric material classes are discussed one by one in dedicated sections and subsections, carefully highlighting the technological solutions on materials growth that have represented a turning point in the research on thermoelectrics. Finally, perspectives and the future of the technology are discussed in the framework of sustainability and environmental compatibility. © 2018 Elsevier B.V.
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| 3. |
- Kroon, Renee, 1982, et al.
(författare)
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Thermally Activated in Situ Doping Enables Solid-State Processing of Conducting Polymers
- 2019
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 1520-5002 .- 0897-4756. ; 31:8, s. 2770-2777
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Tidskriftsartikel (refereegranskat)abstract
- Free-standing bulk structures encompassing highly doped conjugated polymers are currently heavily explored for wearable electronics as thermoelectric elements, conducting fibers, and a plethora of sensory devices. One-step manufacturing of such bulk structures is challenging because the interaction of dopants with conjugated polymers results in poor solution and solid-state processability, whereas doping of thick conjugated polymer structures after processing suffers from diffusion-limited transport of the dopant. Here, we introduce the concept of thermally activated latent dopants for in situ bulk doping of conjugated polymers. Latent dopants allow for noninteractive coprocessing of dopants and polymers, while thermal activation eliminates any thickness-dependent diffusion and activation limitations. Two latent acid dopants were synthesized in the form of thermal acid generators based on aryl sulfonic acids and an o-nitrobenzyl capping moiety. First, we show that these acid dopant precursors can be coprocessed noninteractively with three different polythiophenes. Second, the polymer films were doped in situ through thermal activation of the dopants. Ultimately, we demonstrate that solid-state processing with a latent acid dopant can be readily carried out and that it is possible to dope more than 100 μm-thick polymer films through thermal activation of the latent dopant.
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| 4. |
- Yu, Liyang, 1986, et al.
(författare)
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Diffusion-Limited Crystallization: A Rationale for the Thermal Stability of Non-Fullerene Solar Cells
- 2019
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Ingår i: ACS Applied Materials & Interfaces. - : American Chemical Society (ACS). - 1944-8252 .- 1944-8244. ; 11
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Tidskriftsartikel (refereegranskat)abstract
- © 2019 American Chemical Society. Organic solar cells are thought to suffer from poor thermal stability of the active layer nanostructure, a common belief that is based on the extensive work that has been carried out on fullerene-based systems. We show that a widely studied non-fullerene acceptor, the indacenodithienothiophene-based acceptor ITIC, crystallizes in a profoundly different way as compared to fullerenes. Although fullerenes are frozen below the glass-transition temperature Tg of the photovoltaic blend, ITIC can undergo a glass-crystal transition considerably below its high Tg of ∼180 °C. Nanoscopic crystallites of a low-temperature polymorph are able to form through a diffusion-limited crystallization process. The resulting fine-grained nanostructure does not evolve further with time and hence is characterized by a high degree of thermal stability. Instead, above Tg, the low temperature polymorph melts, and micrometer-sized crystals of a high-temperature polymorph develop, enabled by more rapid diffusion and hence long-range mass transport. This leads to the same detrimental decrease in photovoltaic performance that is known to occur also in the case of fullerene-based blends. Besides explaining the superior thermal stability of non-fullerene blends at relatively high temperatures, our work introduces a new rationale for the design of bulk heterojunctions that is not based on the selection of high-Tg materials per se but diffusion-limited crystallization. The planar structure of ITIC and potentially other non-fullerene acceptors readily facilitates the desired glass-crystal transition, which constitutes a significant advantage over fullerenes, and may pave the way for truly stable organic solar cells.
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