| 1. |
- Alsufyani, Maryam, et al.
(author)
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The effect of aromatic ring size in electron deficient semiconducting polymers for n-type organic thermoelectrics
- 2020
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In: Journal of Materials Chemistry C. - : ROYAL SOC CHEMISTRY. - 2050-7526 .- 2050-7534. ; 8:43, s. 15150-15157
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Journal article (peer-reviewed)abstract
- 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 semiconductors 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 mu V K-1 and maximum Power factors of 0.16 mu W 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.
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| 2. |
- Chen, Hu, et al.
(author)
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Acene Ring Size Optimization in Fused Lactam Polymers Enabling High n-Type Organic Thermoelectric Performance
- 2021
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In: Journal of the American Chemical Society. - : AMER CHEMICAL SOC. - 0002-7863 .- 1520-5126. ; 143:1, s. 260-268
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Journal article (peer-reviewed)abstract
- Three n-type fused lactam semiconducting polymers were synthesized for thermoelectric and transistor applications via a cheap, highly atom-efficient, and nontoxic transition-metal free aldol polycondensation. Energy level analysis of the three polymers demonstrated that reducing the central acene core size from two anthracenes (A-A), to mixed naphthalene-anthracene (A-N), and two naphthalene cores (N-N) resulted in progressively larger electron affinities, thereby suggesting an increasingly more favorable and efficient solution doping process when employing 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (N-DMBI) as the dopant. Meanwhile, organic field effect transistor (OFET) mobility data showed the N-N and A-N polymers to feature the highest charge carrier mobilities, further highlighting the benefits of aryl core contraction to the electronic performance of the materials. Ultimately, the combination of these two factors resulted in N-N, A-N, and A-A to display power factors (PFs) of 3.2 mu W m(-1) K-2, 1.6 mu W m(-1 )K(-2), and 0.3 mu W m(-1) K-2, respectively, when doped with N-DMBI, whereby the PFs recorded for N-N and A-N are among the highest reported in the literature for n-type polymers. Importantly, the results reported in this study highlight that modulating the size of the central acene ring is a highly effective molecular design strategy to optimize the thermoelectric performance of conjugated polymers, thus also providing new insights into the molecular design guidelines for the next generation of high-performance n-type materials for thermoelectric applications.
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| 3. |
- Chen, Zhuoying, et al.
(author)
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Enhanced charge transport by incorporating additional thiophene units in the poly(fluorene-thienyl-benzothiadiazole) polymer
- 2011
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In: Organic electronics. - : Elsevier. - 1566-1199 .- 1878-5530. ; 12:3, s. 461-471
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Journal article (peer-reviewed)abstract
- We report a comparative study of optical properties, structure and morphology, field-effect transistor (FET) and solar cell performance between poly(4-(3,4-dihexyl-2,2-bithiophen-5-yl)-7-(5-(9,9-dioctyl-9H-fluoren-2-yl)-3,4-dihexyl-2,2-bithiophen-5-yl)benzo[c][1,2,5]-thiadiazole) (F8TTBTT), and its predecessor poly((9,9-dioctylfluorene)-2,7-diyl-alt[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2,2 -diyl) (F8TBT). Compared to F8TBT, F8TTBTT has two more thiophene units incorporated in its monomer structure. Such a modification leads to a reduced optical band gap, improved charge injection and significantly enhanced ambipolar field-effect mobilities reaching 5 x 10 (2) cm(2) V (1) s (1) for holes and 4 x 10 (3) cm(2) V (1) s (1) for electrons. The enhanced carrier mobilities are most likely a result of an increased backbone planarization and interchain interaction. As a consequence of ambipolar transport, light-emission was observed from the transistor channel during operation. The reduced band gap and improved charge transport make F8TTBTT an interesting candidate also for solar cell applications. Unoptimized solar cells based on F8TTBTT: PCBM blends were found to exhibit power conversion efficiency under AM 1.5 illumination of similar to 1.54%. (C) 2011 Published by Elsevier B.V.
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| 4. |
- Hallam, Toby, et al.
(author)
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Local Charge Trapping in Conjugated Polymers Resolved by Scanning Kelvin Probe Microscopy
- 2009
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In: Physical Review Letters. - : American Physical Society. - 0031-9007 .- 1079-7114. ; 103:25
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Journal article (peer-reviewed)abstract
- The microstructure of conjugated polymers is heterogeneous on the length scale of individual polymer chains, but little is known about how this affects their electronic properties. Here we use scanning Kelvin probe microscopy with resolution-enhancing carbon nanotube tips to study charge transport on a 100 nm scale in a chain-extended, semicrystalline conjugated polymer. We show that the disordered grain boundaries between crystalline domains constitute preferential charge trapping sites and lead to variations on a 100 nm scale of the carrier concentration under accumulation conditions.
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| 5. |
- Herlogsson, Lars, 1975-, et al.
(author)
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Downscaling of Organic Field-Effect Transistors with a Polyelectrolyte Gate Insulator
- 2008
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In: Advanced Materials. - : Wiley Online. - 0935-9648 .- 1521-4095. ; 20:24, s. 4708-4713
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Journal article (peer-reviewed)abstract
- A polyelectrolyte is used as gate insulator material in organic field-effect transistors with self-aligned inkjet printed sub–micrometer channels. The small separation of the charges in the electric double layer at the electrolyte-semiconductor interface, which builds up in tens of microseconds, provides a very high transverse electric field in the channel that effectively suppresses short-channel effects at low applied gate voltages.
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| 6. |
- Holzer, Isabelle, et al.
(author)
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Side chain engineering in indacenodithiophene-co-benzothiadiazole and its impact on mixed ionic-electronic transport properties
- 2024
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In: Journal of Materials Chemistry C. - : ROYAL SOC CHEMISTRY. - 2050-7526 .- 2050-7534.
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Journal article (peer-reviewed)abstract
- Organic semiconductors are increasingly being decorated with hydrophilic solubilising chains to create materials that can function as mixed ionic-electronic conductors, which are promising candidates for interfacing biological systems with organic electronics. While numerous organic semiconductors, including p- and n-type materials, small molecules and polymers, have been successfully tailored to encompass mixed conduction properties, common to all these systems is that they have been semicrystalline materials. Here, we explore how side chain engineering in the nano-crystalline indacenodithiophene-co-benzothiadiazole (IDTBT) polymer can be used to instil ionic transport properties and how this in turn influences the electronic transport properties. This allows us to ultimately assess the mixed ionic-electronic transport properties of these new IDTBT polymers using the organic electrochemical transistor as the testing platform. Using a complementary experimental and computational approach, we find that polar IDTBT derivatives can be infiltrated by water and solvated ions, they can be electrochemically doped efficiently in aqueous electrolyte with fast doping kinetics, and upon aqueous swelling there is no deterioration of the close interchain contacts that are vital for efficient charge transport in the IDTBT system. Despite these promising attributes, mixed ionic-electronic charge transport properties are surprisingly poor in all the polar IDTBT derivatives. Albeit a "negative" result, this finding clearly contradicts established side chain engineering rules for mixed ionic-electronic conductors, which motivated our continued investigation of this system. We eventually find this anomalous behaviour to be caused by increasing energetic disorder in the polymers with increasing polar side chain content. We have investigated computationally how the polar side chain motifs contribute to this detrimental energetic inhomogeneity and ultimately use the learnings to propose new molecular design criteria for side chains that can facilitate ion transport without impeding electronic transport.
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| 7. |
- Nguyen, Malgorzata, et al.
(author)
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Improving OFF‐State Bias‐Stress Stability in High‐Mobility Conjugated Polymer Transistors with an Anti‐Solvent Treatment
- 2023
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In: Advanced Materials. - : John Wiley & Sons. - 0935-9648 .- 1521-4095. ; 35:16
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Journal article (peer-reviewed)abstract
- Conjugated polymer field-effect transistors are emerging as an enabling technology for flexible electronics due to their excellent mechanical properties combined with sufficiently high charge carrier mobilities and compatibility with large-area, low-temperature processing. However, their electrical stability remains a concern. ON-state (accumulation mode) bias-stress instabilities in organic semiconductors have been widely studied, and multiple mitigation strategies have been suggested. In contrast, OFF-state (depletion mode) bias-stress instabilities remain poorly understood despite being crucial for many applications in which the transistors are held in their OFF-state for most of the time. Here, we present a simple method of using an anti-solvent treatment to achieve significant improvements in OFF-state bias-stress and environmental stability as well as general device performance for one of the best performing polymers, solution-processable indacenodithiophene-co-benzothiadiazole (IDT-BT). IDT-BT is weakly crystalline, and we attribute the notable improvements to an anti-solvent-induced, increased degree of crystallinity, resulting in a lower probability of electron trapping and the removal of charge traps. Our work highlights the importance of the microstructure in weakly crystalline polymer films and offers a simple processing strategy for achieving the reliability required for applications in flexible electronics.
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| 8. |
- Pan, Linfeng, et al.
(author)
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High carrier mobility along the [111] orientation in Cu2O photoelectrodes
- 2024
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In: Nature. - : Springer Nature. - 0028-0836 .- 1476-4687. ; 628:8009, s. 765-770
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Journal article (peer-reviewed)abstract
- Solar fuels offer a promising approach to provide sustainable fuels by harnessing sunlight1,2. Following a decade of advancement, Cu2O photocathodes are capable of delivering a performance comparable to that of photoelectrodes with established photovoltaic materials3,4,5. However, considerable bulk charge carrier recombination that is poorly understood still limits further advances in performance6. Here we demonstrate performance of Cu2O photocathodes beyond the state-of-the-art by exploiting a new conceptual understanding of carrier recombination and transport in single-crystal Cu2O thin films. Using ambient liquid-phase epitaxy, we present a new method to grow single-crystal Cu2O samples with three crystal orientations. Broadband femtosecond transient reflection spectroscopy measurements were used to quantify anisotropic optoelectronic properties, through which the carrier mobility along the [111] direction was found to be an order of magnitude higher than those along other orientations. Driven by these findings, we developed a polycrystalline Cu2O photocathode with an extraordinarily pure (111) orientation and (111) terminating facets using a simple and low-cost method, which delivers 7 mA cm−2 current density (more than 70% improvement compared to that of state-of-the-art electrodeposited devices) at 0.5 V versus a reversible hydrogen electrode under air mass 1.5 G illumination, and stable operation over at least 120 h.
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| 9. |
- Simatos, Dimitrios, et al.
(author)
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Effects of Processing-Induced Contamination on Organic Electronic Devices
- 2023
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In: Small Methods. - : John Wiley and Sons Inc. - 2366-9608. ; 7:11
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Journal article (peer-reviewed)abstract
- Organic semiconductors are a family of pi-conjugated compounds used in many applications, such as displays, bioelectronics, and thermoelectrics. However, their susceptibility to processing-induced contamination is not well understood. Here, it is shown that many organic electronic devices reported so far may have been unintentionally contaminated, thus affecting their performance, water uptake, and thin film properties. Nuclear magnetic resonance spectroscopy is used to detect and quantify contaminants originating from the glovebox atmosphere and common laboratory consumables used during device fabrication. Importantly, this in-depth understanding of the sources of contamination allows the establishment of clean fabrication protocols, and the fabrication of organic field effect transistors (OFETs) with improved performance and stability. This study highlights the role of unintentional contaminants in organic electronic devices, and demonstrates that certain stringent processing conditions need to be met to avoid scientific misinterpretation, ensure device reproducibility, and facilitate performance stability. The experimental procedures and conditions used herein are typical of those used by many groups in the field of solution-processed organic semiconductors. Therefore, the insights gained into the effects of contamination are likely to be broadly applicable to studies, not just of OFETs, but also of other devices based on these materials. © 2023 The Authors.
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| 10. |
- Simatos, Dimitrios, et al.
(author)
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Effects of Processing-Induced Contamination on Organic Electronic Devices
- 2023
-
In: Small Methods. - : Wiley. - 2366-9608. ; 7:11
-
Journal article (peer-reviewed)abstract
- Organic semiconductors are a family of pi-conjugated compounds used in many applications, such as displays, bioelectronics, and thermoelectrics. However, their susceptibility to processing-induced contamination is not well understood. Here, it is shown that many organic electronic devices reported so far may have been unintentionally contaminated, thus affecting their performance, water uptake, and thin film properties. Nuclear magnetic resonance spectroscopy is used to detect and quantify contaminants originating from the glovebox atmosphere and common laboratory consumables used during device fabrication. Importantly, this in-depth understanding of the sources of contamination allows the establishment of clean fabrication protocols, and the fabrication of organic field effect transistors (OFETs) with improved performance and stability. This study highlights the role of unintentional contaminants in organic electronic devices, and demonstrates that certain stringent processing conditions need to be met to avoid scientific misinterpretation, ensure device reproducibility, and facilitate performance stability. The experimental procedures and conditions used herein are typical of those used by many groups in the field of solution-processed organic semiconductors. Therefore, the insights gained into the effects of contamination are likely to be broadly applicable to studies, not just of OFETs, but also of other devices based on these materials.
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