Elucidating Charge Carrier Reactivity, Conversion, and Degradation in n-Doped Oligo- and Poly(benzodifurandione) Jinhyo Hwang, Xiaojuan Ni, Michael F. Espenship, Kan Tang, Junxiang Zhang, et al. Journal of the American Chemical Society, 2025 n-Doped poly(benzodifurandione) (n-PBDF) has gained significant attention due to its solution processability and high electrical conductivity. However, the nature of charge carriers in n-PBDF remains poorly understood. In this study, we investigated a series of oligo(benzodifurandiones) (BFD1, BFD2, and BFD3), using previously reported BFD1 and BFD2 alongside newly synthesized BFD3, with a particular focus on the charged species of BFD3. Neutral BFD3 was successfully reduced to its hydride-adduct anion (BFD3H-), radical anion (BFD3•-), and dianion (BFD32-), the latter two behaving similarly to polarons and bipolarons respectively in n-PBDF. We conducted a characterization of their optical, electrochemical, and structural properties, and examined their interconversion and reactivity. Mass spectrometry analysis and absorption spectroscopy revealed that the BFD32- backbone undergoes degradation when further reduced, with proposed structural assignments for several degradation products. Notably, similar reactivity and degradation pathways were also identified in the polymeric system n-PBDF. These findings provide critical insights into the stability and reactivity of n-type charge carriers in π-conjugated polymers, establishing a foundation for future strategies to optimize doping levels and mitigate degradation in n-type organic electronic materials.
The Excited-State Lifetime of Poly(NDI2OD-T2) Is Intrinsically Short Melissa K. Gish, Chamikara D. Karunasena, Joshua M. Carr, William P. Kopcha, Ann L. Greenaway, et al. Journal of Physical Chemistry C, 2024 Conjugated polymers composed of alternating electron donor and acceptor segments have come to dominate the materials being considered for organic photoelectrodes and solar cells, in large part because of their favorable near-infrared absorption. The prototypical electron-transporting push–pull polymer poly(NDI2OD-T2) (N2200) is one such material. While reasonably efficient organic solar cells can be fabricated with N2200 as the acceptor, it generally fails to contribute as much photocurrent from its absorption bands as the donor with which it is paired. Moreover, transient absorption studies have shown N2200 to have a consistently short excited-state lifetime (∼100 ps) that is dominated by a ground-state recovery. In this paper, we investigate whether these characteristics are intrinsic to the backbone structure of this polymer or if these are extrinsic effects from ubiquitous solution-phase and thin-film aggregates. We compare the solution-phase photophysics of N2200 with those of a pair of model compounds composed of alternating bithiophene (T2) donor and naphthalene diimide (NDI) acceptor units, NDI-T2-NDI and T2-NDI-T2, in a dilute solution. We find that the model compounds have even faster ground-state recovery dynamics (τ = 45, 27 ps) than the polymer (τ = 133 ps), despite remaining molecularly isolated in solution. In these molecules, as in the case of the N2200 polymer, the lowest excited state has a T2 to NDI charge-transfer (CT) character. Electronic-structure calculations indicate that the short lifetime of this state is due to fast nonradiative decay to the ground state (GS) promoted by strong CT–GS electronic coupling and strong electron-vibrational coupling with high-frequency (quantum) normal modes.
Ultra-Narrowband Near-Infrared Responsive J-Aggregates of Fused Quinoidal Tetracyanoindacenodithiophene Qiao He, Aniruddha Basu, Hyojung Cha, Matyas Daboczi, Julianna Panidi, et al. Advanced Materials, 2023 Narrowband photoresponsive molecules are highly coveted in high-resolution imaging, sensing and monochromatic photodetection, especially those extending into the near-infrared (NIR) spectral range. Here we report a new class of J-aggregating materials based on quinoidal indacenodithiophenes (IDT) which exhibit an ultra-narrowband (full width half maxima of 22 nm) NIR absorption peak centered at 770 nm. The spectral width is readily tuned by the length of the solubilising alkyl group, with longer chains resulting in significant spectral narrowing. The J-aggregate behaviour is confirmed by a combination of excited state lifetime measurements and single-crystal X-ray diffraction measurements. Their utility as electron transporting materials is demonstrated in both transistor and phototransistor devices, with the latter demonstrating good response at NIR wavelengths (780 nm) over a range of intensities. This article is protected by copyright. All rights reserved.
N-type polymer semiconductors incorporating heteroannulated benzothiadiazole Xiantao Hu, Aniruddha Basu, Martina Rimmele, Adam V. Marsh, Filip Aniés, et al. Polymer Chemistry, 2022 A series of four n-type semiconducting copolymers containing a 2,1,3-benzothiadiazole (BT) based acceptor annulated with a 2-(1,3-dithiol-2-ylidene)malonitrile group are synthesized and their optoelectronic properties investigated.
Doping Approaches for Organic Semiconductors Alberto D. Scaccabarozzi, Aniruddha Basu, Filip Aniés, Jian Liu, Osnat Zapata-Arteaga, et al. Chemical Reviews, 2022 Electronic doping in organic materials has remained an elusive concept for several decades. It drew considerable attention in the early days in the quest for organic materials with high electrical conductivity, paving the way for the pioneering work on pristine organic semiconductors (OSCs) and their eventual use in a plethora of applications. Despite this early trend, however, recent strides in the field of organic electronics have been made hand in hand with the development and use of dopants to the point that are now ubiquitous. Here, we give an overview of all important advances in the area of doping of organic semiconductors and their applications. We first review the relevant literature with particular focus on the physical processes involved, discussing established mechanisms but also newly proposed theories. We then continue with a comprehensive summary of the most widely studied dopants to date, placing particular emphasis on the chemical strategies toward the synthesis of molecules with improved functionality. The processing routes toward doped organic films and the important doping-processing-nanostructure relationships, are also discussed. We conclude the review by highlighting how doping can enhance the operating characteristics of various organic devices.
Correction to “Electrolyte Immersion Increases Photoconductivity in a Model Polymer Photocathode” WP Kopcha, AA Mohapatra, CM Davis, JR Thurston, EH Suh, B Dong, ... ACS Energy Letters 11 (1), 945-946 , 2025 2025
Electrolyte Immersion Increases Photoconductivity in a Model Polymer Photocathode WP Kopcha, AA Mohapatra, CM Davis, JR Thurston, EH Suh, B Dong, ... ACS Energy Letters 10 (8), 4019-4026 , 2025 2025 Citations: 2
Elucidating Charge Carrier Reactivity, Conversion, and Degradation in n-Doped Oligo-and Poly (benzodifurandione) J Hwang, X Ni, MF Espenship, K Tang, J Zhang, A Basu, S Kuila, ... Journal of the American Chemical Society 147 (22), 19372-19379 , 2025 2025 Citations: 2
The excited-state lifetime of poly (ndi2od-t2) is intrinsically short MK Gish, CD Karunasena, JM Carr, WP Kopcha, AL Greenaway, ... The Journal of Physical Chemistry C 128 (15), 6392-6400 , 2024 2024 Citations: 14
CCDC 2190107: Experimental Crystal Structure Determination: 2, 2'-(4, 4, 9, 9-tetraoctyl-s-indaceno [1, 2-b: 5, 6-b'] bisthiophene 2, 7 (4H, 9H)-diylidene) dipropanedinitrile Q He, A Basu, H Cha, M Daboczi, J Panidi, L Tan, X Hu, CC Huang, ... Cambridge Crystallographic Data Centre , 2023 2023
Ultra‐Narrowband Near‐Infrared Responsive J‐Aggregates of Fused Quinoidal Tetracyanoindacenodithiophene Q He, A Basu, H Cha, M Daboczi, J Panidi, L Tan, X Hu, CC Huang, ... Advanced Materials 35 (11), 2209800 , 2023 2023 Citations: 27
N-type polymer semiconductors incorporating heteroannulated benzothiadiazole X Hu, A Basu, M Rimmele, AV Marsh, F Aniés, Q He, TD Anthopoulos, ... Polymer Chemistry 14 (4), 469-476 , 2023 2023 Citations: 5
Generation of long-lived charges in organic semiconductor heterojunction nanoparticles for efficient photocatalytic hydrogen evolution J Kosco, S Gonzalez-Carrero, CT Howells, T Fei, Y Dong, R Sougrat, ... Nature Energy 7 (4), 340-351 , 2022 2022 Citations: 403
N-type polymer semiconductors incorporating para, meta, and ortho-carborane in the conjugated backbone F Aniés, Z Qiao, MI Nugraha, A Basu, TD Anthopoulos, N Gasparini, ... Polymer 240, 124481 , 2022 2022 Citations: 19
Y6 Organic Thin-Film Transistors with Electron Mobilities of 2.4 cm² V⁻ ¹ s⁻ ¹ via Microstructural Tuning E Gutiérrez Fernández, AD Scaccabarozzi, A Basu, E Solano, ... 2022
Doping-induced decomposition of organic semiconductors: a caveat to the use of Lewis acid p-dopants G Rotas, G Antoniou, P Papagiorgis, A Basu, J Panidi, P Ufimkin, ... Journal of Materials Chemistry C 10 (35), 12751-12764 , 2022 2022 Citations: 8
Y6 Organic Thin‐Film Transistors with Electron Mobilities of 2.4 cm 2 V −1 s −1 via Microstructural Tuning E Gutierrez‐Fernandez, AD Scaccabarozzi, A Basu, E Solano, ... Advanced science 9 (1), 2104977 , 2022 2022 Citations: 62
Doping Approaches for Organic Semiconductors AD Scaccabarozzi^, A Basu^, (^equal contribution), F Aniés, J Liu, ... Chemical Reviews 122 (4), 4420–4492 , 2021 2021 Citations: 473
Adduct-based p-doping of organic semiconductors N Sakai, R Warren, F Zhang, S Nayak, J Liu, SV Kesava, YH Lin, ... Nature Materials 20 (9), 1248-1254 , 2021 2021 Citations: 84
The effect of alkyl spacers on the mixed ionic‐electronic conduction properties of n‐type polymers IP Maria, BD Paulsen, A Savva, D Ohayon, R Wu, R Hallani, A Basu, ... Advanced Functional Materials 31 (14), 2008718 , 2021 2021 Citations: 144
The influence of alkyl group regiochemistry and backbone fluorination on the packing and transistor performance of N-cyanoimine functionalised indacenodithiophenes T Hodsden, KJ Thorley, A Basu, AJP White, C Wang, W Mitchell, ... Materials Advances 2 (5), 1706-1714 , 2021 2021 Citations: 12
Long-range exciton diffusion in molecular non-fullerene acceptors Y Firdaus, VM Le Corre, S Karuthedath, W Liu, A Markina, W Huang, ... Nature communications 11 (1), 5220 , 2020 2020 Citations: 415
Laser Patterning of Boron Carbon Nitride Electrodes for Flexible Micro-Supercapacitor with Remarkable Electrochemical Stability/Capacity I Karbhal, A Basu, A Patrike, MV Shelke Carbon 171, 750-757 , 2020 2020 Citations: 64
Understanding Charge Transport in High‐Mobility p‐Doped Multicomponent Blend Organic Transistors AD Scaccabarozzi, F Scuratti, AJ Barker, A Basu, AF Paterson, Z Fei, ... Advanced Electronic Materials, 2000539 , 2020 2020 Citations: 25
Impact of p-type doping on charge transport in blade-coated small-molecule: polymer blend transistors A Basu*, MR Niazi, AD Scaccabarozzi, H Faber, Z Fei, DH Anjum, ... Journal of Materials Chemistry C 8 (43), 15368-15376 , 2020 2020 Citations: 30
MOST CITED SCHOLAR PUBLICATIONS
Doping Approaches for Organic Semiconductors AD Scaccabarozzi^, A Basu^, (^equal contribution), F Aniés, J Liu, ... Chemical Reviews 122 (4), 4420–4492 , 2021 2021 Citations: 473
Long-range exciton diffusion in molecular non-fullerene acceptors Y Firdaus, VM Le Corre, S Karuthedath, W Liu, A Markina, W Huang, ... Nature communications 11 (1), 5220 , 2020 2020 Citations: 415
Single crystal hybrid perovskite field-effect transistors W Yu, F Li, L Yu, MR Niazi, Y Zou, D Corzo, A Basu, C Ma, S Dey, ... Nature communications 9 (1), 5354 , 2018 2018 Citations: 414
Generation of long-lived charges in organic semiconductor heterojunction nanoparticles for efficient photocatalytic hydrogen evolution J Kosco, S Gonzalez-Carrero, CT Howells, T Fei, Y Dong, R Sougrat, ... Nature Energy 7 (4), 340-351 , 2022 2022 Citations: 403
The effect of alkyl spacers on the mixed ionic‐electronic conduction properties of n‐type polymers IP Maria, BD Paulsen, A Savva, D Ohayon, R Wu, R Hallani, A Basu, ... Advanced Functional Materials 31 (14), 2008718 , 2021 2021 Citations: 144
CO 2 Laser Direct Written MOF-Based Metal-Decorated and Heteroatom-Doped Porous Graphene for Flexible All-Solid-State Microsupercapacitor with Extremely … A Basu, K Roy, N Sharma, S Nandi, R Vaidhyanathan, S Rane, C Rode, ... ACS applied materials & interfaces 8 (46), 31841-31848 , 2016 2016 Citations: 105
Addition of the Lewis Acid Zn (C6F5) 2 Enables Organic Transistors with a Maximum Hole Mobility in Excess of 20 cm2 V− 1 s− 1 AF Paterson, L Tsetseris, R Li, A Basu, H Faber, AH Emwas, J Panidi, ... Advanced Materials 31 (27), 1900871 , 2019 2019 Citations: 101
Starch (Tapioca) to carbon dots: an efficient green approach to an on–off–on photoluminescence probe for fluoride ion sensing A Basu, A Suryawanshi, B Kumawat, A Dandia, D Guin, SB Ogale Analyst 140 (6), 1837-1841 , 2015 2015 Citations: 96
Highly Stable Laser‐Scribed Flexible Planar Microsupercapacitor Using Mushroom Derived Carbon Electrodes P Yadav^, A Basu^, (^equal contribution), A Suryawanshi, O Game, ... Advanced Materials Interfaces 3 (11), 1600057 , 2016 2016 Citations: 87
Adduct-based p-doping of organic semiconductors N Sakai, R Warren, F Zhang, S Nayak, J Liu, SV Kesava, YH Lin, ... Nature Materials 20 (9), 1248-1254 , 2021 2021 Citations: 84
Laser Patterning of Boron Carbon Nitride Electrodes for Flexible Micro-Supercapacitor with Remarkable Electrochemical Stability/Capacity I Karbhal, A Basu, A Patrike, MV Shelke Carbon 171, 750-757 , 2020 2020 Citations: 64
Y6 Organic Thin‐Film Transistors with Electron Mobilities of 2.4 cm 2 V −1 s −1 via Microstructural Tuning E Gutierrez‐Fernandez, AD Scaccabarozzi, A Basu, E Solano, ... Advanced science 9 (1), 2104977 , 2022 2022 Citations: 62
Evaluation of n-type ternary metal oxide NiMn2O4 nanomaterial for humidity sensing Y Gawli, S Badadhe, A Basu, D Guin, MV Shelke, S Ogale Sensors and Actuators B: Chemical 191, 837-843 , 2014 2014 Citations: 55
Core Fluorination Enhances Solubility and Ambient Stability of an IDT‐Based n‐Type Semiconductor in Transistor Devices T Hodsden, KJ Thorley, J Panidi, A Basu, AV Marsh, H Dai, AJP White, ... Advanced Functional Materials 30 (17), 2000325 , 2020 2020 Citations: 39
Impact of p-type doping on charge transport in blade-coated small-molecule: polymer blend transistors A Basu*, MR Niazi, AD Scaccabarozzi, H Faber, Z Fei, DH Anjum, ... Journal of Materials Chemistry C 8 (43), 15368-15376 , 2020 2020 Citations: 30
Ultra‐Narrowband Near‐Infrared Responsive J‐Aggregates of Fused Quinoidal Tetracyanoindacenodithiophene Q He, A Basu, H Cha, M Daboczi, J Panidi, L Tan, X Hu, CC Huang, ... Advanced Materials 35 (11), 2209800 , 2023 2023 Citations: 27
Colossal Tunneling Electroresistance in Co‐Planar Polymer Ferroelectric Tunnel Junctions M Kumar, DG Georgiadou, A Seitkhan, K Loganathan, E Yengel, H Faber, ... Advanced Electronic Materials, 1901091 , 2019 2019 Citations: 26
Understanding Charge Transport in High‐Mobility p‐Doped Multicomponent Blend Organic Transistors AD Scaccabarozzi, F Scuratti, AJ Barker, A Basu, AF Paterson, Z Fei, ... Advanced Electronic Materials, 2000539 , 2020 2020 Citations: 25
Catalyst free novel synthesis of graphene and its application in high current OFET and phototransistor based on P3HT/G composite P Yadav, C Chanmal, A Basu, L Mandal, J Jog, S Ogale RSC Advances 3 (39), 18049-18054 , 2013 2013 Citations: 22
F-Doped carbon nano-onion films as scaffold for highly efficient and stable Li metal anodes: a novel laser direct-write process D Puthusseri, M Wahid, A Basu, R Babar, M Kabir, S Ogale Nanoscale 10 (16), 7630-7638 , 2018 2018 Citations: 21
