Search for: All records

Abstract Chemical doping is an important approach to manipulating charge-carrier concentration and transport in organic semiconductors (OSCs)^1–3and ultimately enhances device performance^4–7. However, conventional doping strategies often rely on the use of highly reactive (strong) dopants^8–10, which are consumed during the doping process. Achieving efficient doping with weak and/or widely accessible dopants under mild conditions remains a considerable challenge. Here, we report a previously undescribed concept for the photocatalytic doping of OSCs that uses air as a weak oxidant (p-dopant) and operates at room temperature. This is a general approach that can be applied to various OSCs and photocatalysts, yielding electrical conductivities that exceed 3,000 S cm^–1. We also demonstrate the successful photocatalytic reduction (n-doping) and simultaneous p-doping and n-doping of OSCs in which the organic salt used to maintain charge neutrality is the only chemical consumed. Our photocatalytic doping method offers great potential for advancing OSC doping and developing next-generation organic electronic devices. 

This well-studied polymer system does not conform to existing design criteria for imparting mixed conduction. The reasons for this anomalous behaviour are unravelled and used to outline more robust design criteria for new organic semiconductors. 

This perspective offers insights from discussions conducted during the Telluride Science meeting on organic mixed ionic and electronic conductors, outlining the challenges associated with understanding the behavior of this intriguing materials class. 

Polymeric mixed ionic-electronic conductors (MIECs) combine aspects of conjugated polymers, polymer electrolytes, and polyelectrolytes to simultaneously transport and couple ionic and electronic charges, opening exciting new applications in energy storage and conversion, bioelectronics, and display technologies. The many applications of polymeric MIECs lead to a wide range of transport conditions. Ionic and electronic transport are directly coupled through electrochemical doping, while the mechanisms of ionic and electronic transport depend on distinctly different chemical functionality, (macro)molecular structure, and morphology. Despite this, ionic and electronic transport are surprisingly tunable, independent of one another. We review the various types of polymeric MIECs, the mechanisms of ionic and electronic charge transport across conditions, and the interrelations between the two, with special emphasis on the unique aspects of polymeric MIEC transport phenomena. Expected final online publication date for the Annual Review of Materials Science, Volume 51 is August 2021. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates. 

N-type semiconducting polymers have been recently utilized in thermoelectric devices, however they have typically exhibited low electrical conductivities and poor device stability, in contrast to p-type semiconductors, which have been much higher performing. This is due in particular to the n-type semiconductor's low doping efficiency, and poor charge carrier mobility. Strategies to enhance the thermoelectric performance of n-type materials include optimizing the electron affinity (EA) with respect to the dopant to improve the doping process and increasing the charge carrier mobility through enhanced molecular packing. Here, we report the design, synthesis and characterization of fused electron-deficient n-type copolymers incorporating the electron withdrawing lactone unit along the backbone. The polymers were synthesized using metal-free aldol condensation conditions to explore the effect of enlarging the central phenyl ring to a naphthalene ring, on the electrical conductivity. When n-doped with N-DMBI, electrical conductivities of up to 0.28 S cm −1 , Seebeck coefficients of −75 μV K −1 and maximum Power factors of 0.16 μW m −1 K −2 were observed from the polymer with the largest electron affinity of −4.68 eV. Extending the aromatic ring reduced the electron affinity, due to reducing the density of electron withdrawing groups and subsequently the electrical conductivity reduced by almost two orders of magnitude. 

Abstract Conducting polymers, such as thep-doped poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), have enabled the development of an array of opto- and bio-electronics devices. However, to make these technologies truly pervasive, stable and easily processable,n-doped conducting polymers are also needed. Despite major efforts, non-type equivalents to the benchmark PEDOT:PSS exist to date. Here, we report on the development of poly(benzimidazobenzophenanthroline):poly(ethyleneimine) (BBL:PEI) as an ethanol-basedn-type conductive ink. BBL:PEI thin films yield ann-type electrical conductivity reaching 8 S cm⁻¹, along with excellent thermal, ambient, and solvent stability. This printablen-type mixed ion-electron conductor has several technological implications for realizing high-performance organic electronic devices, as demonstrated for organic thermoelectric generators with record high power output andn-type organic electrochemical transistors with a unique depletion mode of operation. BBL:PEI inks hold promise for the development of next-generation bioelectronics and wearable devices, in particular targeting novel functionality, efficiency, and power performance. 

Abstract A new approach to control the n‐doping reaction of organic semiconductors is reported using surface‐functionalized gold nanoparticles (f‐AuNPs) with alkylthiols acting as the catalyst only upon mild thermal activation. To demonstrate the versatility of this methodology, the reaction of the n‐type dopant precursor N‐DMBI‐H with several molecular and polymeric semiconductors at different temperatures with/without f‐AuNPs, vis‐à‐vis the unfunctionalized catalyst AuNPs, was investigated by spectroscopic, morphological, charge transport, and kinetic measurements as well as, computationally, the thermodynamic of catalyst activation. The combined experimental and theoretical data demonstrate that while f‐AuNPs is inactive at room temperature both in solution and in the solid state, catalyst activation occurs rapidly at mild temperatures (~70 °C) and the doping reaction completes in few seconds affording large electrical conductivities (~10–140 S cm⁻¹). The implementation of this methodology enables the use of semiconductor+dopant+catalyst solutions and will broaden the use of the corresponding n‐doped films in opto‐electronic devices such as thin‐film transistors, electrochemical transistors, solar cells, and thermoelectrics well as guide the design of new catalysts.