Reported here is a new high electron affinity acceptor end group for organic semiconductors, 2,1,3‐benzothiadiazole‐4,5,6‐tricarbonitrile (TCNBT). An n‐type organic semiconductor with an indacenodithiophene (IDT) core and TCNBT end groups was synthesized by a sixfold nucleophilic substitution with cyanide on a fluorinated precursor, itself prepared by a direct arylation approach. This one‐step chemical modification significantly impacted the molecular properties: the fluorinated precursor, TFBT IDT, a poor ambipolar semiconductor, was converted into TCNBT IDT, a good n‐type semiconductor. The electron‐deficient end group TCNBT dramatically decreased the energy of the highest occupied and lowest unoccupied molecular orbitals (HOMO/LUMO) compared to the fluorinated analogue and improved the molecular orientation when utilized in n‐type organic field‐effect transistors (OFETs). Solution‐processed OFETs based on TCNBT IDT exhibited a charge‐carrier mobility of up to μe≈0.15 cm2 V−1 s−1 with excellent ambient stability for 100 hours, highlighting the benefits of the cyanated end group and the synthetic approach.
The power conversion efficiencies (PCEs) of single‐junction organic solar cells (OSCs) have surpassed 19%, owing to the emerging Y‐series nonfullerene acceptors (NFAs). Undoubtedly, the power and flexibility of chemical design has been a strong driver for this rapid efficiency improvement in the OSC field. Over the course of the past 3 years, a variety of modifications have been made to the structure of the Y6 acceptor, and a large number of Y‐series NFAs have been reported to further improve performance. Herein, we present our insights into the rationale behind the Y6 acceptor and discuss the design principles toward high‐performance Y‐series NFAs. It is clear that structural modifications through choice of heteroatom, soluble chains, π spacers, central cores, and end groups alter the material characteristics and properties, contributing to distinctive photovoltaic performance. Subsequently, we analyze various design strategies of Y‐series‐containing materials, including polymerized small‐molecule acceptors (PSMA), non‐fused‐ring acceptors (NFRA), and all‐fused‐ring acceptors (AFRA). This review is expected to be of value in providing effective molecular design strategies for high‐performance NFAs in future innovations.
Novel lead and bismuth dipyrido complexes have been synthesized and characterized by single-crystal X-ray diffraction, which shows their structures to be directed by highly oriented π-stacking of planar fully conjugated organic ligands. Optical band gaps are influenced by the identity of both the organic and inorganic component. Density functional theory calculations show optical excitation leads to exciton separation between inorganic and organic components. Using UV-vis, photoluminescence, and X-ray photoemission spectroscopies, we have determined the materials' frontier energy levels and show their suitability for photovoltaic device fabrication by use of electron- and hole-transport materials such as TiO2 and spiro-OMeTAD respectively. Such organic/inorganic hybrid materials promise greater electronic tunability than the inflexible methylammonium lead iodide structure through variation of both the metal and organic components.
Small band gap molecular semiconductors are of interest for the development of transparent electronics. Here we report two near-infrared (NIR), n-type small molecule semiconductors, based upon an acceptor−donor−acceptor (A-D-A) approach. We show that the inclusion of molecular spacers between the strong-electron-accepting end group, 2,1,3benzothiadiazole-4,5,6-tricarbonitrile, and the donor core affords semiconductors with very low band gaps down to 1 eV. Both materials were synthesized by a one-pot, 6-fold nucleophilic displacement of a fluorinated precursor by cyanide. Significant differences in solid-state ordering and charge carrier mobility are observed depending on the nature of the spacer, with a thiophene spacer resulting in solution processed organic field-effect transistors (OFETs) exhibiting excellent electron mobility up to 1.1 cm 2 V −1 s −1 . The use of silver nanowires as the gate electrode enables the fabrication of a semitransparent OFET device with an average visible transmission of 71% in the optical spectrum.
We investigate the dependence of
charge yields on the driving force
for photoinduced electron transfer in a series of all-small-molecule,
semiconducting films made from indacenodithiophene nonfullerene acceptors
(IDT NFAs). In contrast to reports of efficient, barrierless charge
separation at near zero driving force for NFA-containing organic photovoltaics,
we find that barrierless charge separation occurs only if the driving
force is sufficient to overcome the Coulomb potential, ≥300
meV, based on time-resolved microwave conductivity and PL quenching
measurements of 5 mmolal sensitized and 700 mmolal blended films comprising
IDT NFAs paired with three different donors. This discrepancy with
recent literature is caused by a difference in the way that we calculate
driving force. Far from being semantic, the driving force calculation
is crucial because its value controls the mechanisms needed to explain
experimental observations. We provide a candid assessment of the uncertainties
for our methods and popular ones used in the literature and emphasize
the importance of standardizing methods across this field.
Compared to fullerene based electron acceptors, n-type organic semiconductors, so-called non-fullerene acceptors (NFAs), possess some distinct advantages, such as readily tuning of optical absorption and electronic energy levels, strong absorption in the visible region and good morphological stability for flexible electronic devices. The design and synthesis of new NFAs have enabled the power conversion efficiencies (PCEs) of organic photovoltaic (OPV) devices to increase to around 19%. This review summarises the important breakthroughs that have contributed to this progress, focusing on three classes of NFAs, i.e. perylene diimide (PDI), diketopyrrolopyrrole (DPP) and acceptor–donor–acceptor (A-D-A) based NFAs. Specifically, the PCEs of PDI, DPP, and A-D-A series based non-fullerene OPVs have been reported up to 11%, 13% and 19%, respectively. Structure–property relationships of representative NFAs and their impact on OPV performances are discussed. Finally, we consider the remaining challenges and promising directions for achieving high-performing NFAs.
Reported here is a new high electron affinity acceptor end group for organic semiconductors, 2,1,3‐benzothiadiazole‐4,5,6‐tricarbonitrile (TCNBT). An n‐type organic semiconductor with an indacenodithiophene (IDT) core and TCNBT end groups was synthesized by a sixfold nucleophilic substitution with cyanide on a fluorinated precursor, itself prepared by a direct arylation approach. This one‐step chemical modification significantly impacted the molecular properties: the fluorinated precursor, TFBT IDT, a poor ambipolar semiconductor, was converted into TCNBT IDT, a good n‐type semiconductor. The electron‐deficient end group TCNBT dramatically decreased the energy of the highest occupied and lowest unoccupied molecular orbitals (HOMO/LUMO) compared to the fluorinated analogue and improved the molecular orientation when utilized in n‐type organic field‐effect transistors (OFETs). Solution‐processed OFETs based on TCNBT IDT exhibited a charge‐carrier mobility of up to μe≈0.15 cm2 V−1 s−1 with excellent ambient stability for 100 hours, highlighting the benefits of the cyanated end group and the synthetic approach.
Two benzothiadiazole derivatives annulated with 2-(1,3-dithiol-2-ylidene)malonitrile in the 4,5-position were prepared by a one-step procedure, and investigated as end-groups in non-fullerene acceptors for indoor photovoltaic applications.
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