n-Type organic semiconducting polymers: stability limitations, design considerations and applications

Journal of Materials Chemistry C, Journal Year: 2021, Volume and Issue: 9(26), P. 8099 - 8128

Published: Jan. 1, 2021

This review outlines the design strategies which aim to develop high performing n-type materials in fields of organic thin film transistors (OTFT), electrochemical (OECT) and thermoelectrics (OTE). Figures merit for each application limitations obtaining these are set out, challenges with achieving consistent comparable measurements addressed. We present a thorough discussion materials, particularly their ambient operational instability, suggest synthetic methods overcome these. instability originates from oxidation negative polaron semiconductor (OSC) by water oxygen, potentials commonly fall within window OSCs, consequently require LUMO level deeper than ∼-4 eV material stability. Recent detailed principles discussed explain how modifications can enhance performance. be achieved through number strategies, including utilising an electron deficient acceptor-acceptor backbone repeat unit motif, introducing electron-withdrawing groups or heteroatoms, rigidification planarisation polymer increasing conjugation length. By studying fundamental have been employed date, this highlights path development promising polymers OSC applications future.

Language: Английский

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Cyano-Functionalized Bithiophene Imide-Based n-Type Polymer Semiconductors: Synthesis, Structure–Property Correlations, and Thermoelectric Performance

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(3), P. 1539 - 1552

Published: Jan. 14, 2021

n-Type polymers with deep-positioned lowest unoccupied molecular orbital (LUMO) energy levels are essential for enabling n-type organic thin-film transistors (OTFTs) high stability and thermoelectrics (OTEs) doping efficiency promising thermoelectric performance. Bithiophene imide (BTI) its derivatives have been demonstrated as acceptor units constructing high-performance polymers. However, the electron-rich thiophene moiety in BTI leads to elevated LUMOs resultant hence limits their performance intrinsic stability. Herein, we addressed this issue by introducing strong electron-withdrawing cyano functionality on derivatives. We successfully overcome synthetic challenges developed a series of novel building blocks, CNI, CNTI, CNDTI, which show substantially higher electron deficiencies than does BTI. On basis these acceptor–acceptor type homopolymers copolymers were synthesized featured greatly suppressed (−3.64 −4.11 eV) versus that (−3.48 control polymer PBTI. Their resulted improved OTFTs more efficient n-doping OTEs corresponding highest electrical conductivity 23.3 S cm–1 power factor ∼10 μW m–1 K–2. The among values reported solution-processed molecularly n-doped new CNDTI offer remarkable platform polymers, study demonstrates cyano-functionalization is very effective strategy developing deep-lying electronic devices.

Language: Английский

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Recent advances in n-type and ambipolar organic semiconductors and their multi-functional applications

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(4), P. 1331 - 1381

Published: Jan. 1, 2023

A comprehensive summary and deep insights into the synthesis, characterization multi-functional device applications of n-type ambipolar organic semiconductors are provided in this study.

Language: Английский

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Progress of Conjugated Polymers as Emerging Thermoelectric Materials

Progress in Polymer Science, Journal Year: 2022, Volume and Issue: 129, P. 101548 - 101548

Published: April 13, 2022

Thanks to the combined efforts of scientists in several research fields, preceding decade has witnessed considerable progress use conjugated polymers as emerging thermoelectric materials leading significant improvements performance and demonstration a number diverse applications. Despite these recent advances, systematic assessments impact molecular design on properties are scarce. Although reviews marginally highlight role chemical structure, understanding structure-performance relationships is still fragmented. An in-depth relationship between structure will enable rational next-generation polymers. To this end, review showcases state-of-the-art polymers, discusses relationships, suggests strategies for improving that go beyond design, highlights some most impressive applications

Language: Английский

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A Distannylated Monomer of a Strong Electron‐Accepting Organoboron Building Block: Enabling Acceptor–Acceptor‐Type Conjugated Polymers for n‐Type Thermoelectric Applications

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(29), P. 16184 - 16190

Published: May 7, 2021

Abstract Acceptor–acceptor (A‐A) copolymerization is an effective strategy to develop high‐performance n‐type conjugated polymers. However, the development of A‐A type polymers challenging due synthetic difficulty. Herein, a distannylated monomer strong electron‐deficient double B←N bridged bipyridine (BNBP) unit readily synthesized and used by Stille polycondensation. The resulting show ultralow LUMO energy levels −4.4 eV, which among lowest value reported for organoboron After n‐doping, exhibit electric conductivity 7.8 S cm −1 power factor 24.8 μW m K −2 . This performance best polymer thermoelectric materials. These results demonstrate great potential thermoelectrics.

Language: Английский

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Efficient and air-stable n-type doping in organic semiconductors

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(11), P. 3842 - 3872

Published: Jan. 1, 2023

In this review, the key factors that determined air stability and doping efficiency of n-type doped organic semiconductors were summarized, together with discussion their applications in electronics.

Language: Английский

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An n‐Type Polythiophene Derivative with Excellent Thermoelectric Performance

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(18)

Published: March 3, 2023

Typical n-type conjugated polymers are based on fused-ring electron-accepting building blocks. Herein, we report a non-fused-ring strategy to design polymers, i.e. introducing electron-withdrawing imide or cyano groups each thiophene unit of polythiophene backbone. The resulting polymer, n-PT1, shows low LUMO/HOMO energy levels -3.91 eV/-6.22 eV, high electron mobility 0.39 cm2 V-1 s-1 and crystallinity in thin film. After n-doping, n-PT1 exhibits excellent thermoelectric performance with an electrical conductivity 61.2 S cm-1 power factor (PF) 141.7 μW m-1 K-2 . This PF is the highest value reported so far for this first time derivatives be used organic thermoelectrics. due its superior tolerance doping. work indicates that without fused rings low-cost high-performance polymers.

Language: Английский

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Multi-heterojunctioned plastics with high thermoelectric figure of merit

Nature, Journal Year: 2024, Volume and Issue: 632(8025), P. 528 - 535

Published: July 24, 2024

Language: Английский

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An n‐Type Conjugated Polymer with Low Crystallinity for High‐Performance Organic Thermoelectrics

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 8, 2024

Abstract Conjugated polymers (CPs) with low crystallinity are promising candidates for application in organic thermoelectrics (OTEs), particularly flexible devices, because the disordered structures of these CPs can effectively accommodate dopants and ensure robust resistance to bending. However, n‐doped usually exhibit poor thermoelectric performance, which hinders development high‐performance generators. Herein, we report an n‐type CP (ThDPP‐CNBTz) comprising two acceptor units: a thiophene‐flanked diketopyrrolopyrrole cyano‐functionalized benzothiadiazole. ThDPP‐CNBTz shows LUMO energy level below −4.20 eV features crystallinity, enabling high doping efficiency. Moreover, dual‐acceptor design enhances polaron delocalization, resulting good performance. After n‐doping, exhibits average electrical conductivity ( σ ) 50.6 S cm −1 maximum power factor (PF) 126.8 μW m K −2 , is among highest values reported solution‐processed date. Additionally, OTE device based on doped PF 70 ; also remarkable bending strain, only marginal change after 600 cycles. The findings presented this work will advance devices particular.

Language: Английский

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Persistent Conjugated Backbone and Disordered Lamellar Packing Impart Polymers with Efficient n‐Doping and High Conductivities

Advanced Materials, Journal Year: 2020, Volume and Issue: 33(2)

Published: Nov. 30, 2020

Abstract Solution‐processable highly conductive polymers are of great interest in emerging electronic applications. For p‐doped polymers, conductivities as high a nearly 10 5 S cm −1 have been reported. In the case n‐doped they often fall well short values noted above, which might be achievable, if much higher charge‐carrier mobilities determined could realized combination with densities. This is part due to inefficient doping and dopant ions disturbing ordering limiting efficient charge transport ultimately achievable conductivities. Here, that achieve conductivity more than 90 by simple solution‐based co‐deposition method Two conjugated rigid planar backbones, but disordered crystalline structures, exhibit surprising structural tolerance to, excellent miscibility with, commonly used n‐dopants. These properties allow both concentrations mobility carriers simultaneously resulting electrical thermoelectric performance.

Language: Английский

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