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Abstract Chemical doping is an important approach to manipulating charge-carrier concentration and transport in organic semiconductors (OSCs)1–3and ultimately enhances device performance4–7. However, conventional doping strategies often rely on the use of highly reactive (strong) dopants8–10, 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.
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On‐Demand Catalysed n‐Doping of Organic Semiconductors
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.
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- Award ID(s):
- 2223922
- PAR ID:
- 10557746
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 63
- Issue:
- 33
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Katz, Howard E (Ed.)Abstract Doping of organic semiconductors has served as an effective method to achieve high electrical conductivity and large thermoelectric power factor. This is of importance to the development of flexible/wearable electronics and green energy‐harvesting technologies. The doping impact of the Lewis acid tris (pentafluorophenyl) borane (BCF) on the thermoelectric performance of poly(2‐(4,4′‐bis(2‐methoxyethoxy)‐5′‐methyl‐[2,2′‐bithiophen]‐5‐yl)‐5‐methylthieno[3,2‐b]thiophene (pgBTTT), a thiophene‐based polymer featuring oligoethylene glycol side chains is investigated. Tetrafluorotetracyanoquinodimethane (F4TCNQ), a well‐established dopant, is utilized as a comparison; however, its inability to co‐dissolve with pgBTTT in less polar solvents hinders the attainment of higher doping levels. Consequently, a comparative study is performed on the thermoelectric behavior of pgBTTT doped with BCF and F4TCNQ at a very low doping level. Subsequent investigation is carried out with BCF at higher doping levels. Remarkably, at 50 wt% BCF doping level, the highest power factor of 223 ± 4 µW m−1K2is achieved with an electrical conductivity of 2180 ± 360 S cm−1and a Seebeck coefficient of 32 ± 1.3 µV K−1. This findings not only contribute valuable insights to the dopant interactions with oxygenated side chain polymers but also open up new avenues for high conductivity thermoelectric polymers in flexible electronic applications.more » « less
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Abstract Organic mixed ionic–electronic conductors (OMIECs) have varied performance requirements across a diverse application space. Chemically doping the OMIEC can be a simple, low‐cost approach for adapting performance metrics. However, complex challenges, such as identifying new dopant materials and elucidating design rules, inhibit its realization. Here, these challenges are approached by introducing a new n‐dopant, tetrabutylammonium hydroxide (TBA‐OH), and identifying a new design consideration underpinning its success. TBA‐OH behaves as both a chemical n‐dopant and morphology additive in donor acceptor co‐polymer naphthodithiophene diimide‐based polymer, which serves as an electron transporting material in organic electrochemical transistors (OECTs). The combined effects enhance OECT transconductance, charge carrier mobility, and volumetric capacitance, representative of the key metrics underpinning all OMIEC applications. Additionally, when the TBA+counterion adopts an “edge‐on” location relative to the polymer backbone, Coulombic interaction between the counterion and polaron is reduced, and polaron delocalization increases. This is the first time such mechanisms are identified in doped‐OECTs and doped‐OMIECs. The work herein therefore takes the first steps toward developing the design guidelines needed to realize chemical doping as a generic strategy for tailoring performance metrics in OECTs and OMIECs.more » « less
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Thin films of amorphous small molecule semiconductors are widely used in organic light emitting displays and have promising applications in solar cells and thermoelectric devices. Adding dopants increases the conductivity of organic semiconductors, but high concentrations of dopants can disrupt their structural ordering, alter the shape of the electronic density of states in the material, and increase the effects of Coulomb interactions on charge transport. Electrical doping of the solution processable hole-transport material 2,2′,7,7′-tetrakis[ N , N -di(4-methoxyphenyl)amino]-9,9′-spirobifluorene (spiro-OMeTAD) was studied with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 TCNQ) as a p-type dopant. Infiltration of F 4 TCNQ from the vapor phase into films of spiro-OMeTAD provided a route to highly doped films with up to 39 ± 2 mol% doping. Structural characterization confirmed that the films remain amorphous even at the highest doping levels with no apparent phase separation. We quantitatively determined the carrier concentration using UV-Vis spectroscopy to interpret the evolution of the electrical conductivity. Over the range of carrier concentrations (10 19 –10 20 1 cm −3 ), the electrical conductivity increased no more than linearly with carrier concentration, while the thermopower had a small increase with carrier concentration. The trends in conductivity and thermopower were related to the unique electronic structure of spiro-OMeTAD, which is able to support two carriers per molecule. Temperature-dependent conductivity measurements were used to further analyze the transport mechanism.more » « less
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Chemical doping is widely used to manipulate the electrical and thermoelectric properties of organic semiconductors, yet intelligent design of polymer–dopant systems remains elusive. It is challenging to predict the electrical and thermoelectric properties of doped organic semiconductors due to the large number of variables impacting these properties, including film morphology, dopant and polymer energetics, dopant size, and degree of polaron delocalization. Herein, a series of dopants with varying sizes and electron affinities (EAs) are combined with polymers of differing ionization energies (IEs) to investigate how the difference between polymer IE and dopant EA influences the doping efficiency and electrical conductivity, and how the dopant size influences the thermoelectric properties. Our experiments demonstrate that at low doping levels the doping efficiency strongly depends on the difference between the polymer IE and dopant EA; the effectiveness of doping on increasing electrical conductivity drastically decreases at high loadings for the molybdenum dithiolene complexes, while FeCl 3 remains effective at high loadings; and the large molybdenum complexes lead to more delocalized polarons as compared to FeCl 3 . To take advantage of the complementary doping characteristics of the molybdenum complexes and FeCl 3 , both dopants are employed simultaneously to reach high power factors at relatively low dopant concentrations.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1002/anie.202407273
