Revisiting doping mechanisms of n-type organic materials with N-DMBI for thermoelectric applications: Photo-activation, thermal activation, and air stability

Bardagot, Olivier; Aumaître, Cyril; Monmagnon, Anthony; Pécaut, Jacques; Bayle, Ariane; Demadrille, Renaud

doi:10.1063/5.0047637

Cited by 26 publications

(39 citation statements)

References 30 publications

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“…Our quantitative data complement and confirm those reported in the literature, demonstrating that DMBI-Ox is produced in non-negligible amounts during the timespan normally necessary for sample handling in doping experiments . Nonetheless, DMBI-H has been used successfully under a variety of experimental conditions with comparable performances. ,− …”

Section: Characterization Of Dmbi-h Stabilitysupporting

confidence: 85%

“…There could be different explanations for such a phenomenon. On the one side, the presence of water could stabilize one or more of the charged intermediates that Demadrille hypothesized, thus slowing down the reaction . Conversely, water could react with one of the transient species, again leading to more stable intermediates.…”

Section: Characterization Of Dmbi-h Stabilitymentioning

confidence: 99%

“…The former is demonstrated, but the latter is questionable. Very recently, Wang and Demadrille, among others, disclosed the limited stability of DMBI-H while dissolved in organic solvents, including those commonly employed for processing. − Such observation is somewhat surprising as it is apparently conflicting with the fact that most authors carry out doping experiments in air with commercially available samples of DMBI-H and without mentioning specific purification and/or preliminary characterizations. ,− …”

Section: Introductionmentioning

confidence: 99%

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Unexpected Enhancement of Molecular n-Doping Efficiency in Polymer Thin Films by a Degradation Product

Pallini

Mattiello

Cassinelli

et al. 2022

ACS Appl. Energy Mater.

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Molecular doping of conjugated polymers is extremely desirable to control charge density gradients and shape the electric field across polymer electronic devices, including highly efficient organic solar cells. It is also a fundamental requirement for organic thermoelectrics and a powerful strategy to boost charge injection and transport properties in transistors. Yet, currently available doping approaches are far from offering a suitable level of control, particularly in the case of n-type doping. We here reveal that part of this limitation lies in the lack of understanding of dominant factors in doping efficiency. In particular, we highlight the key role played by very small amounts of a specific decomposition product formed during processing of the widely used molecular dopant 4-(2,3-dihydro-1,3dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (DMBI-H) in influencing the n-type conductivity in polymer blends. We show that such an overlooked decomposition product acts as a nucleating agent for a new crystalline phase of DMBI-H, with the overall effect of boosting the electrical conductivity of the final doped polymer films. Such results, confirmed by control experiments performed with a different nucleating agent, focus on the crucial role played by the solid-state microstructure in molecular doped semiconductors and offer ground for a significant change in design guidelines for molecular doping strategies.

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Section: Characterization Of Dmbi-h Stabilitysupporting

confidence: 85%

Section: Characterization Of Dmbi-h Stabilitymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Unexpected Enhancement of Molecular n-Doping Efficiency in Polymer Thin Films by a Degradation Product

Pallini

Mattiello

Cassinelli

et al. 2022

ACS Appl. Energy Mater.

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“…This is possibly due to the existence of the cation species in N-DMBI-doped samples, as reported in literature. [36][37][38] Next, we employed OFET as the platform to evaluate the effect of doping on the electrical properties of the semiconductor. TGBC devices with doped semiconductors as active layers were fabricated.…”

Section: P-/n-doping Of Pbbt-4t-2f At Low Doping Levels and Ofet Char...mentioning

confidence: 99%

Selective doping of a single ambipolar organic semiconductor to obtain P- and N-type semiconductors

Chen

Zhao

Chen

et al. 2022

Matter

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“…Chemical dopants can be introduced into OMIECs to modify their coloration. For instance, electron‐rich chemical dopants such as 4(1,3 dimethyl‐2,3‐dihydro‐1H‐benzoimidazol‐2‐yl)phenyl)dimethylamine (N‐DMBI) [ 127 ] or amines [ 18 ] can be used to donate electrons into electron‐deficient OMIECs. The injection of electrons into the LUMO of n‐type OMIECs increases the optical bandgap of the OMIEC, thereby bleaching the absorption of the backbone.…”

Section: Omiec Property Changesmentioning

confidence: 99%

Mixed Ionic–Electronic Conduction, a Multifunctional Property in Organic Conductors

et al. 2022

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consumption and sensing as well as high-energy-density batteries for energy storage. Recently, interest in developing systems that interface seamlessly with the human body (e.g., wearables, braincomputer interfaces, and soft robots) has driven the development of soft, organic, and biomimetic materials that emulate the functions of their inorganic counterparts. Beyond emulation, these materials are unique because they provide an opportunity to embody such multifunctional properties within the material itself, rather than relying on device design. These multifunctional properties are intrinsic to organic mixed ionic electronic conductors (OMIECs), that is, once synthesized and processed, OMIECs can serve as the active component of multiple devices (be it transistors, sensors, energy-storage devices, etc.), where essentially the material is the device.OMIECs generally consist of a conjugated backbone for electronic conduction as well as sidechains to facilitate ionic intercalation from the operational electrolyte and to aid in solvation in processing solvents. [1] Organic chemistry provides a large toolbox in the molecular design of the backbone, side chains, and other additives, resulting in an almost infinite design space for the corresponding materials properties: energy levels, electronic and ionic conductivity, optical, volume, and moduli. Additionally, one or more of these properties can be modified during device operation, thereby transducing an input (e.g., ionic) into an output (e.g., electronic), allowing OMIECs to be used for a variety of applications including sensors, transistors, optoelectronic devices, energy-storage electrodes, and actuators. The multifunctionality of OMIECs is illustrated in Figure 1 to highlight their versatility in design and their ability to respond to a variety of stimuli.The underlying and unifying phenomena behind these property changes arise from the large modulation in electronic and ionic charge density in the bulk of the OMIEC. This modulation in turn results in second-order effects such as modulations in electrochemical potential (electron energy levels), electronic and ionic transport, capacitance, free volume, optical bandgap, and modulus. Tuning these properties throughout the bulk of the material enables new design parameters that were previously untapped in traditional electronic devices where Organic mixed ionic-electronic conductors (OMIECs) have gained recent interest and rapid development due to their versatility in diverse applications ranging from sensing, actuation and computation to energy harvesting/ storage, and information transfer. Their multifunctional properties arise from their ability to simultaneously participate in redox reactions as well as modulation of ionic and electronic charge density throughout the bulk of the material. Most importantly, the ability to access charge states with deep modulation through a large extent of its density of states and physical volume of the material enables OMIEC-based devices to display exciting new characteristics...

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Revisiting doping mechanisms of n-type organic materials with N-DMBI for thermoelectric applications: Photo-activation, thermal activation, and air stability

Cited by 26 publications

References 30 publications

Unexpected Enhancement of Molecular n-Doping Efficiency in Polymer Thin Films by a Degradation Product

Unexpected Enhancement of Molecular n-Doping Efficiency in Polymer Thin Films by a Degradation Product

Selective doping of a single ambipolar organic semiconductor to obtain P- and N-type semiconductors

Mixed Ionic–Electronic Conduction, a Multifunctional Property in Organic Conductors

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