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Organic electrochemical transistors (OECTs) and OECT-based circuitry offer great potential in bioelectronics, wearable electronics and artificial neuromorphic electronics because of their exceptionally low driving voltages (10 mS) and biocompatibility1–5. However, the successful realization of critical complementary logic OECTs is currently limited by temporal and/or operational instability, slow redox processes and/or switching, incompatibility with high-density monolithic integration and inferior n-type OECT performance6–8. Here we demonstrate p- and n-type vertical OECTs with balanced and ultra-high performance by blending redox-active semiconducting polymers with a redox-inactive photocurable and/or photopatternable polymer to form an ion-permeable semiconducting channel, implemented in a simple, scalable vertical architecture that has a dense, impermeable top contact. Footprint current densities exceeding 1 kA cm−2 at less than ±0.7 V, transconductances of 0.2–0.4 S, short transient times of less than 1 ms and ultra-stable switching (>50,000 cycles) are achieved in, to our knowledge, the first vertically stacked complementary vertical OECT logic circuits. This architecture opens many possibilities for fundamental studies of organic semiconductor redox chemistry and physics in nanoscopically confined spaces, without macroscopic electrolyte contact, as well as wearable and implantable device applications.

Conducting polymers (CPs) with high conductivity and solution processability have made great advances since the pioneering work on doped polyacetylenesup1-3/sup, thus creating the new field of 'organic synthetic metals,sup4/sup. Various high-performance CPs have been realized, which enable the applications of several organic electronic devicessup5,6/sup. Nevertheless, most CPs exhibit hole-dominant (p-type) transport behavioursup7,8/sup, whereas the development of n-type analogues lags far behind and only a few exhibit metallic state, typically limited by low doping efficiency and ambient instability. Here we present a facilely synthesized highly conductive n-type polymer poly(benzodifurandione) (PBFDO). The reaction combines oxidative polymerization and in situ reductive n-doping, greatly increasing the doping efficiency, and a doping level of almost 0.9 charges per repeating unit can be achieved. The resultant polymer exhibits a breakthrough conductivity of more than 2,000 S cmsup-1/supwith excellent stability and an unexpected solution processability without extra side chains or surfactants. Furthermore, detailed investigations on PBFDO show coherent charge-transport properties and existence of metallic state. The benchmark performances in electrochemical transistors and thermoelectric generators are further demonstrated, thus paving the way for application of the n-type CPs in organic electronics.

Charge carrier nonradiative recombination (NRR) caused by interface defects and nonoptimal energy level alignment is the primary factor restricting the performance improvement of perovskite solar cells (PSCs). Interfacial modification is a vital strategy to restrain NRR and enable high-performance PSCs. We report here two interfacial materials, PhI-TPA and BTZI-TPA, consisting of phthalimide and a 2,1,3-benzothiadiazole-5,6-dicarboxylicimide core, respectively. The difunctionalized BTZI-TPA with imide and thiadiazole shows higher hole mobility, better aligned energy levels, and stronger interaction with uncoordinated Pb

Despite their multifaceted advantages, inverted perovskite solar cells (PSCs) still suffer from lower power conversion efficiencies (PCEs) than their regular counterparts, which is largely due to recombination energy losses (

Cyano substitution is vital to the molecular design of polymer semiconductors toward highly efficient organic solar cells. However, how regioselectivity impacts relevant optoelectronic properties in cyano-substituted bithiophene systems remain poorly understood. Three regioisomeric cyano-functionalized dialkoxybithiophenes BTHH, BTHT, and BTTT with head-to-head, head-to-tail, and tail-to-tail linkage, respectively, were synthesized and characterized in this work. The resulting polymer semiconductors (PBDTBTs) based on these building blocks were prepared accordingly. The regiochemistry and property relationships of PBDTBTs were investigated in detail. The BTHH moiety has a higher torsional barrier than the analogs BTHT and BTTT, and the regiochemistry of dialkoxybithiophenes leads to fine modulation in the optoelectronic properties of these polymers, such as optical absorption, band gap, and energy levels of frontier molecular orbitals. Organic field-effect transistors based on PBDTBTHH had higher hole mobility (4.4 × 10−3 cm2/(V·s)) than those (ca. 10−4 cm2/(V·s)) of the other two polymer analogs. Significantly different short-circuit current densities and fill factors were obtained in polymer solar cells using PBDTBTs as the electron donors. Such difference was probed in greater detail by performing space-charge-limited current mobility, thin-film morphology, and transient photocurrent/photovoltage characterizations. The findings highlight that the BTHH unit is a promising building block for the construction of polymer donors for high-performance organic photovoltaic cells. Graphical abstract

As one of the polymer modification strategies, carboxylate functionalization has proved effective in downshifting the energy levels and enhancing polymer crystallinity and aggregation. However, high-performance carboxylate-containing polymers are still limited for organic solar cells (OSCs), especially with open-circuit voltage (

Self-assembled molecules (SAMs) have shown great potential in replacing bulk charge selective contact layers in high-performance perovskite solar cells (PSCs) due to their low material consumption and simple processing. Herein, we design and synthesize a series of donor-acceptor (D-A) type SAMs (MPA-BT-CA, MPA-BT-BA, and MPA-BT-RA, where MPA is 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline; BT is benzo[c][1,2,5]-thiadiazole; CA is 2-cyanoacrylic acid, BA is benzoic acid, RA is rhodanine-3-propionic acid) with distinct anchoring groups, which show dramatically different properties. MPA-BT-CA with CA anchoring groups exhibited stronger dipole moments and formed a homogeneous monolayer on the indium tin oxide (ITO) surface by adopting an upstanding self-assembling mode. However, the MPA-BT-RA molecules tend to aggregate severely in solid state due to the sp3 hybridization of the carbon atom on the RA group, which is not favorable for achieving a long-range ordered self-assembled layer. Consequently, benefiting from high dipole moment, as well as dense and uniform self-assembled film, the device based on MPA-BT-CA yielded a remarkable power conversion efficiency (PCE) of 21.81%. Encouragingly, an impressive PCE approaching 20% can still be obtained for the MPA-BT-CA-based PSCs as the device area is increased to 0.80 cm2. Our work sheds light on the design principles for developing hole selecting SAMs, which will pave a way for realizing highly efficient, flexible, and large-area PSCs.

The development of n-type organic semiconductors critically relies on the design and synthesis of highly electron-deficient building blocks with good solubility and small steric hindrance. We report here a strongly electron-deficient dithienylpyrazinediimide (TPDI) and its n-type semiconducting polymers. The pyrazine substitution leads to the resulting polymers with much lower-lying lowest unoccupied molecular orbital (LUMO) levels and improved backbone planarity compared to the reported dithienylbenzodiimide (TBDI)- and fluorinated dithienylbenzodiimide (TFBDI)-based polymer analogues, thus yielding n-type transport character with an electron mobility up to 0.44 cm

Inverted-structure metal halide perovskite solar cells (PSCs) have attractive advantages like low-temperature processability and outstanding device stability. The two-step sequential deposition method shows the benefits of easy fabrication and decent performance repeatability. Nevertheless, it is still challenging to achieve high-performance inverted PSCs with similar or equal power conversion efficiencies (PCEs) compared to the regular-structure counterparts via this deposition method. Here, an improved two-step sequential deposition technique is demonstrated via treating the bottom organic hole-selective layer with the binary modulation system composed of a polyelectrolyte and an ammonium salt. Such improved sequential deposition method leads to the spontaneous refinement of up and buried interfaces for the perovskite films, contributing to high film quality with significantly reduced defect density and better charge transportation. As a result, the optimized PSCs show a large enhancement in the open-circuit voltage by 100 mV and a dramatic lift in the PCE from 18.1% to 23.4%, delivering the current state-of-the-art performances for inverted PSCs. Moreover, good operational and thermal stability is achieved upon the improved inverted PSCs. This innovative strategy helps gain a deeper insight into the perovskite crystal growth and defect modulation in the inverted PSCs based on the two-step sequential deposition method.

The development of n-type organic electrochemical transistors (OECTs) lags far behind their p-type counterparts. In order to address this dilemma, we report here two new fused bithiophene imide dimer (f-BTI2)-based n-type polymers with a branched methyl end-capped glycol side chain, which exhibit good solubility, low-lying LUMO energy levels, favorable polymer chain orientation, and efficient ion transport property, thus yielding a remarkable OECT electron mobility (μe ) of up to ≈10-2 cm2 V-1 s-1 and volumetric capacitance (C*) as high as 443 F cm-3 , simultaneously. As a result, the f-BTI2TEG-FT-based OECTs deliver a record-high maximum geometry-normalized transconductance of 4.60 S cm-1 and a maximum μC* product of 15.2 F cm-1 V-1 s-1 . The μC* figure of merit is more than one order of magnitude higher than that of the state-of-the-art n-type OECTs. The emergence of f-BTI2TEG-FT brings a new paradigm for developing high-performance n-type polymers for low-power OECT applications.

This study describes the development of a series of strong electron-deficient acceptor units, namely, fluorenone imide (FOI) and its derivatives, functionalized with various electron-withdrawing groups, which are developed

n-Type semiconducting polymers with high thermoelectric performance remain challenging due to the scarcity of molecular design strategy, limiting their applications in organic thermoelectric (OTE) devices. Herein, we provide a new approach to enhance the OTE performance of n-doped polymers by introducing acceptor-acceptor (A-A) type backbone bearing branched ethylene glycol (EG) side chains. When doped with 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (N-DMBI), the A-A homopolymer PDTzTI-TEG exhibits n-type electrical conductivity (σ) up to 34 S cm

Solution-processed hole contact materials, as an indispensable component in perovskite solar cells (PSCs), have been widely studied with consistent progress achieved. One bottleneck for the commercialization of PSCs is the lack of hole contact materials with high performance, cost-effective preparation, and green-solvent processability. Therefore, the development of versatile hole contact materials is of great significance. Herein, we report two novel donor-acceptor (D-A)-type hole contact molecules (FMPA-BT-CA and 2FMPA-BT-CA) with low cost and alcohol-based processability by utilizing a fluorination strategy. We showed that the fluorine atoms lead to the lowered highest occupied molecular orbital (HOMO) energy levels and larger dipole moments for FMPA-BT-CA and 2FMPA-BT-CA. Moreover, fluorination also improves the buried interfacial interaction between hole contacts and perovskite. As a result, a remarkable power conversion efficiency (PCE) of 22.37% along with good light stability could be achieved for green-solvent-processed FMPA-BT-CA-based inverted PSC devices, demonstrating the great potential of environmentally compatible hole contacts for highly efficient PSCs.

The remarkable advance of all-polymer solar cells (all-PSCs) achieved in the past decades is primarily powered by the innovation of polymer acceptors. However, most of high-performance all-PSCs are dominantly fabricated with halogenated solvents, which are detrimental to human bodies and the environment. Herein, eco-friendly solvent-processed all-PSCs were developed, based on wide-bandgap polymer poly[4,8-bis(5-(2-ethylhexylthio)thiophen-2-yl)-benzo-[1,2-b;4,5-b']dithiophene-alt-2,5-di(butyloctylthiophen-2-yl) -thiazolo[5,4-d]thiazole] (PSTZ) as donor and newly synthesized narrow-bandgap polymer 5,6-dicyano-2,1,3-benzothiadiazole indacenodithiophene (DCNBT-IDT) as acceptor. When processed with o-xylene and THF, PSTZ : DCNBT-IDT-based all-PSCs yielded remarkable power conversion efficiencies of 7.23 and 8.77 % with high short-circuit currents of 12.94 and 14.12 mA cm-2 , respectively. The results indicated that the utilization of an all-polymer blend based on narrow polymer acceptor and compatible polymer donor is an effective strategy for advancing eco-friendly solvent-processed all-PSCs.

The development of high-performance n-type polymer semiconductors is powered by the design and synthesis of electron-deficient building blocks with optimized physicochemical properties. By meticulously installing an imide group onto fluorene and its cyanated derivative, we report here two very electron-deficient building blocks, imide-functionalized fluorenone (FOI) and its cyanated derivative (FCNI), both featuring a deep-lying lowest unoccupied molecular orbital energy level down to -4.05 eV and highly coplanar framework, endowing them ideal units for constructing n-type polymers. Thus, a series of polymers are built from them, exhibiting unipolar n-type transport character with a highest electron mobility of 0.11 cm

Summary There is an urgent demand for all-polymer organic solar cells (AP-OSCs) to gain higher efficiency. Here, we successfully improve the performance to 16.09% by introducing a small amount of BN-T, a B←N-type polymer acceptor, into the PM6:PY-IT blend. It has been found that BN-T makes the active layer, based on the PM6:PY-IT:BN-T ternary blend, more crystalline but meanwhile slightly reduces the phase separation, leading to enhancement of both exciton harvesting and charge transport. From a thermodynamic viewpoint, BN-T prefers to reside between PM6 and PY-IT, and the fraction of this fine-tunes the morphology. Besides, a significantly reduced nonradiative energy loss occurs in the ternary blend, along with the coexistence of energy and charge transfer between the two acceptors. The progressive performance facilitated by these improved properties demonstrates that AP-OSCs can possibly comparably efficient with those based on small molecule acceptors, further enhancing the competitiveness of this device type.

In this work, a fused polycyclic aromatic hydrocarbon (PAH) core was introduced to construct hole-transporting materials (HTMs) for perovskite solar cells (PSCs). It was found that with the extende...

n-Type polymers with deep-positioned lowest unoccupied molecular orbital (LUMO) energy levels are essential for enabling n-type organic thin-film transistors (OTFTs) with high stability and n-type organic thermoelectrics (OTEs) with high doping efficiency and promising thermoelectric performance. Bithiophene imide (BTI) and its derivatives have been demonstrated as promising acceptor units for constructing high-performance n-type polymers. However, the electron-rich thiophene moiety in BTI leads to elevated LUMOs for the resultant polymers and hence limits their n-type performance and intrinsic stability. Herein, we addressed this issue by introducing strong electron-withdrawing cyano functionality on BTI and its derivatives. We have successfully overcome the synthetic challenges and developed a series of novel acceptor building blocks, CNI, CNTI, and CNDTI, which show substantially higher electron deficiencies than does BTI. On the basis of these novel building blocks, acceptor-acceptor type homopolymers and copolymers were successfully synthesized and featured greatly suppressed LUMOs (-3.64 to -4.11 eV) versus that (-3.48 eV) of the control polymer PBTI. Their deep-positioned LUMOs resulted in improved stability in OTFTs and more efficient n-doping in OTEs for the corresponding polymers with a highest electrical conductivity of 23.3 S cm

Low-cost and eco-friendly hole-transport materials (HTMs) are exceedingly desirable for the practical application of perovskite solar cells (PVSCs). Here, a traditional bidentate ligand (1,10-phenanthroline), widely used as a chelating agent for bioorganic reagents and probes, is incorporated into an HTM to afford M1. Such a planar bidentate ligand at the central core of the HTM can facilitate π–π stacking and enable chelation to Pb2+ ion defects and thus achieve efficient passivation at the M1/perovskite interface, contributing to reduced recombination loss. When employed as an HTM in inverted PVSCs without dopants, bidentate-ligand-based M1 yields a high power conversion efficiency (PCE) of 20.14%, which is significantly higher than that (18.32%) of the M0 analogue that contains phenanthrene. More importantly, green solvent processing (ethyl acetate) of M1 achieves a PCE of 19.21%, which is among the highest values reported in PVSCs with a green-solvent-processable HTM. Besides, the facile one-step synthesis route reduces the cost to 45 $ gram−1 for M1, which is cheaper than the most reported HTMs for high-efficiency PVSCs without dopants. These findings demonstrate the potential of bidentate ligands in developing cost-effective and eco-friendly HTMs toward highly efficient PVSCs.

Organic photovoltaics (OPVs) are one of the most promising technologies to power indoor electronic devices. However, the limited types and design strategies of medium band-gap acceptor materials hinder the development of indoor OPVs. Currently, the state-of-the-art non-fullerene acceptors (NFAs) are Y6 and its derivatives, which are based on an A–DA′D–A structure. In this paper, we report the modification of the Y6 structure by replacing Y6's D unit (thieno[3,2-b]thiophene) with benzothiophene, and synthesize two novel NFAs (LBT-DF and LBT-SCl) for indoor applications. The use of the benzothiophene unit reduces the intermolecular charge transfer effect, thus blue-shifting the absorption spectra and up-shifting the LUMO energy levels of the NFAs. As a result, LBT-SCl achieves a higher Voc and thus PCE (up to 25.1%) than Y6 (22.2%) under indoor conditions. Interestingly, these two NFAs exhibit a non-planar aromatic structure, which is rarely observed in the published NFAs, because a better coplanar molecular configuration is usually considered as the critical factor in realizing high PCE. Different from the above mentioned molecular design concept, we find that non-planar structure acceptors also have great potential in OPVs. Our work provides an effective OPV material design guideline for developing high-performance indoor OPVs and also opens a new direction for the design of NFAs.

Different from the commonly studied non-fullerene electron acceptors with large fused backbone architecture and tedious synthesis steps, non-fused ring electron acceptors are attractive for organic solar cells (OSC) due to their simple synthesis and comparable device performance. However, it is key to choose appropriate building blocks for constructing non-fused ring electron acceptors to achieve high-performance OSCs. Herein, two simple non-fused ring electron acceptors, TPDC-4F and BTIC-4F, which possess the same terminals and 4H-cyclopenta[1,2-b:5,4-b′]dithiophene unit coupled with different electron-deficient diketone central units, are synthesized. TPDC-4F with a thieno[3,4-c]pyrrole-4,6-dione core exhibits a smaller optical bandgap of 1.42 eV, downshifted lowest unoccupied molecular orbital energy levels, higher electron mobility, and enhanced molecular packing order in neat thin films as compared to BTIC-4F with a 2,2′-bithiophene-3,3′-dicarboxyimide core. As a result, the OSC based on TPDC-4F with stronger molecular packing yielded a high power conversion efficiency (PCE) of 13.35% with a Voc of 0.852 V, which is one of the best values ever reported in non-fused ring electron acceptors-based binary OSCs with Voc over 0.85 V, and is better than that of OSC based on the BTIC-4F with weaker molecular stacking (PCE = 12.04%). This work demonstrates the application of electron-deficient diketone units in efficient non-fused ring electron acceptors and provides molecular design guidance for high-performance OSCs.

The structural rigidity of fused units in the polymer backbone, in addition to the resulting stabilizing effect of the quinoidal structure, and tunable electronic properties have played a key role in promoting highly-ordered π-stacking moieties, exhibiting promising charge carrier mobilities. The electron-deficient thiazole moiety shows high planarity and effective π–π stacking, which leads to the reduction in the energy levels of the highest occupied and lowest unoccupied molecular orbitals (HOMO/LUMO), and ideally enhances the electron charge mobility. Four heterocycle-based monomers BTzS, BTzSe, DTS, and DTG based on fused bithiazole and dithiophene units incorporated with sulfur, selenium, silicon, and germanium as the bridging atoms were synthesized and characterized. The monomers were copolymerized with the electron-rich alkylated thienylenevinylene (TV) unit to afford copolymers P1–P4. The thermal, optical, and electrochemical properties and crystallinity of the copolymers were thoroughly investigated. Extensive OFET device optimization using different solvents and annealing temperatures resulted in the best charge mobility of 0.09 cm2 V−1 s−1 for the electron-deficient bithiazole BTzS copolymer P1 and 0.36 cm2 V−1 s−1 for the DTS copolymer P3.

n-Type organic mixed ionic-electronic conductors (OMIECs) with high electron mobility are scarce and highly challenging to develop. As a result, the figure-of-merit (µC*) of n-type organic electrochemical transistors (OECTs) lags far behind the p-type analogs, restraining the development of OECT-based low-power complementary circuits and biosensors. Here, two n-type donor-acceptor (D-A) polymers based on fused bithiophene imide dimer f-BTI2 as the acceptor unit and thienylene-vinylene-thienylene (TVT) as the donor co-unit are reported. The cyanation of TVT enables polymer f-BTI2g-TVTCN with simultaneously enhanced ion-uptake ability, film structural order, and charge-transport property. As a result, it is able to obtain a high volumetric capacitance (C*) of 170 ± 22 F cm