Both fluorine and ester substituted monothiophene yielded a novel thiophene derivative FE-T. The resulting polymer donor S1 enabled single-junction non-fullerene solar cell with over 16% efficiency.

Development of high-performance unipolar n-type organic semiconductors still remains as a great challenge. In this work, all-acceptor bithiophene imide-based ladder-type small molecules BTI n and semiladder-type homopolymers PBTI n ( n = 1-5) were synthesized, and their structure-property correlations were studied in depth. It was found that Pd-catalyzed Stille coupling is superior to Ni-mediated Yamamoto coupling to produce polymers with higher molecular weight and improved polymer quality, thus leading to greatly increased electron mobility (μ). Due to their all-acceptor backbone, these polymers all exhibit unipolar n-type transport in organic thin-film transistors, accompanied by low off-currents (10-10 A), large on/off current ratios (10), and small threshold voltages (∼15-25 V). The highest μ, up to 3.71 cm V s, is attained from PBTI1 with the shortest monomer unit. As the monomer size is extended, the μ drops by 2 orders to 0.014 cm V s for PBTI5. This monotonic decrease of μ was also observed in their homologous BTI n small molecules. This trend of mobility decrease is in good agreement with the evolvement of disordered phases within the film, as revealed by Raman spectroscopy and X-ray diffraction measurements. The extension of the ladder-type building blocks appears to have a large impact on the motion freedom of the building blocks and the polymer chains during film formation, thus negatively affecting film morphology and charge carrier mobility. The result indicates that synthesizing building blocks with more extended ladder-type backbone does not necessarily lead to improved mobilities. This study marks a significant advance in the performance of all-acceptor-type polymers as unipolar electron transporting materials and provides useful guidelines for further development of (semi)ladder-type molecular and polymeric semiconductors for applications in organic electronics.

Chemical doping is a key process for investigating charge transport in organic semiconductors and improving certain (opto)electronic devices 1-9 . N-(electron)doping is fundamentally more challenging than p-(hole)doping and typically achieves very low doping efficiency (η) <10% 1,10 . An efficient molecular n-dopant should simultaneously exhibit a high reducing power and air stability for broad applicability 1,5,6,9,11 , which is very challenging. Here we show a general concept of catalysed n-doping of organic semiconductors using air-stable precursor-type molecular dopants. Incorporation of a transition metal as vapor-deposited nanoparticles (e.g. Pt, Au, Pd) or solution-processable 2 organometallic complexes (e.g. Pd 2 (dba) 3 ) catalyses the reaction, as assessed by experimental and theoretical evidence, enabling drastically increased η in a much shorter doping time and high electrical conductivities >100 S cm −1 12 . This methodology has technological implications for realizing improved semiconductor devices and offers a broad exploration space of ternary systems comprising catalysts, molecular dopants, and semiconductors, thus opening new opportunities in n-doping research and applications.N-doping of organic semiconductors is important for developing light-emitting diodes 1,6-9 , solar cells 7,8 , thin-film transistors 10 , and thermoelectric devices 12,13 . Although solution-based ndoping is widely investigated, only few air-stable n-dopants have been developed (Fig. S1), with the most prominent being organic hydrides 5,9,14-18 such as benzoimidazole derivatives, dimers of organic radicals 11,19,20 such as nineteen-electron organometallic sandwich compounds, and mono-/multi-valent anions 8,21,22 such as OH − , F − and Ox 2− . These air-stable dopants have a deep ionization potential (IP) in their initial forms, thus, cannot directly transfer electrons to n-dope organic semiconductors with a low electron affinity (EA). For anions, it was shown that dispersion into small anhydrous clusters enables sufficiently high donor levels for n-doping organic semiconductors with EAs up to 2.4 eV 8 . Hydride and dimer dopant precursors (or referred as precursor-type dopants) most undergo a C-H and C-C bond cleavage reaction, respectively, to generate active-doping-species in situ before electron transfer can occur [23][24][25][26] . Thus, their reducing strength and reaction kinetics are strongly affected by the thermodynamics and the activation energies of the doping reaction [23][24][25][26] . If the activation energy to the product is reduced, it is expected that the reaction rate, and extent of doping, will greatly increase (Fig. 1a). 3Transition metal (TM) catalysed C-H and C-C bond cleavage reactions are widely used in organic synthesis, with the most common TMs belonging to group 8-11 elements and the catalysts in the form of nanoparticles (NPs) and organometallic complexes 27,28 . Nanoparticle size, supporting material, and chemical structure of the complex can greatly affect catalytic activities. Thus, an i...

As a key component in perovskite solar cells (PVSCs), hole-transporting materials (HTMs) have been extensively explored and studied. Aiming to meet the requirements for future commercialization of PVSCs, HTMs which can enable excellent device performance with low cost and eco-friendly processability are urgently needed but rarely reported. In this work, a traditional anchoring group (2-cyanoacrylic acid) widely used in molecules for dye-sensitized solar cells is incorporated into donor–acceptor-type HTMs to afford MPA-BT-CA, which enables effective regulation of the frontier molecular orbital energy levels, interfacial modification of an ITO electrode, efficient defect passivation toward the perovskite layer, and more importantly alcohol solubility. Consequently, inverted PVSCs with this low-cost HTM exhibit excellent device performance with a remarkable power conversion efficiency (PCE) of 21.24% and good long-term stability in ambient conditions. More encouragingly, when processing MPA-BT-CA films with the green solvent ethanol, the corresponding PVSCs also deliver a substantial PCE as high as 20.52% with negligible hysteresis. Such molecular design of anchoring group-based materials represents great progress for developing efficient HTMs which combine the advantages of low cost, eco-friendly processability, and high performance. We believe that such design strategy will pave a new path for the exploration of highly efficient HTMs applicable to commercialization of PVSCs.

Narrow bandgap (1.37-1.46 eV) polymers incorporating a head-to-head linkage containing 3-alkoxy-3'-alkyl-2,2'-bithiophene are synthesized. The head-to-head linkage enables polymers with sufficient solubility and the noncovalent sulfur-oxygen interaction affords polymers with high degree of backbone planarity and film ordering. When integrated into polymer solar cells, the polymers show a promising power conversion efficiency approaching 10%.

A novel imide‐functionalized arene, di(fluorothienyl)thienothiophene diimide (f‐FBTI2), featuring a fused backbone functionalized with electron‐withdrawing F atoms, is designed, and the synthetic challenges associated with highly electron‐deficient fluorinated imide are overcome. The incorporation of f‐FBTI2 into polymer affords a high‐performance n‐type semiconductor f‐FBTI2‐T, which shows a reduced bandgap and lower‐lying lowest unoccupied molecular orbital (LUMO) energy level than the polymer analog without F or with F‐functionalization on the donor moiety. These optoelectronic properties reflect the distinctive advantages of fluorination of electron‐deficient acceptors, yielding “stronger acceptors,” which are desirable for n‐type polymers. When used as a polymer acceptor in all‐polymer solar cells, an excellent power conversion efficiency of 8.1% is achieved without any solvent additive or thermal treatment, which is the highest value reported for all‐polymer solar cells except well‐studied naphthalene diimide and perylene diimide‐based n‐type polymers. In addition, the solar cells show an energy loss of 0.53 eV, the smallest value reported to date for all‐polymer solar cells with efficiency > 8%. These results demonstrate that fluorination of imide‐functionalized arenes offers an effective approach for developing new electron‐deficient building blocks with improved optoelectronic properties, and the emergence of f‐FBTI2 will change the scenario in terms of developing n‐type polymers for high‐performance all‐polymer solar cells.

Significant progress has been made in nonfullerene small molecule acceptors (NF‐SMAs) that leads to a consistent increase of power conversion efficiency (PCE) of nonfullerene organic solar cells (NF‐OSCs). To achieve better compatibility with high‐performance NF‐SMAs, the direction of molecular design for donor polymers is toward wide bandgap (WBG), tailored properties, and preferentially ecofriendly processability for device fabrication. Here, a weak acceptor unit, methyl 2,5‐dibromo‐4‐fluorothiophene‐3‐carboxylate (FE‐T), is synthesized and copolymerized with benzo[1,2‐b:4,5‐b′]dithiophene (BDT) to afford a series of nonhalogenated solvent processable WBG polymers P1‐P3 with a distinct side chain on FE‐T. The incorporation of FE‐T leads to polymers with a deep highest occupied molecular orbital (HOMO) level of −5.60−5.70 eV, a complementary absorption to NF‐SMAs, and a planar molecular conformation. When combined with the narrow bandgap acceptor ITIC‐Th, the solar cell based on P1 with the shortest methyl chain on FE‐T achieves a PCE of 11.39% with a large V oc of 1.01 V and a J sc of 17.89 mA cm−2. Moreover, a PCE of 12.11% is attained for ternary cells based on WBG P1, narrow bandgap PTB7‐Th, and acceptor IEICO‐4F. These results demonstrate that the new FE‐T is a highly promising acceptor unit to construct WBG polymers for efficient NF‐OSCs.

Head-to-head (HH) bithiophenes are typically avoided in polymer semiconductors since they engender undesirable steric repulsions, leading to a twisted backbone. While introducing electron-donating alkoxy chains can lead to intramolecular noncovalent S···O interactions, this comes at the cost of elevating the HOMOs and compromising polymer solar cell (PSC) performance. To address the limitation, a novel HH bithiophene featuring an electron-withdrawing ester functionality, 3-alkoxycarbonyl-3′-alkoxy-2,2′-bithiophene (TETOR), is synthesized. Single crystal diffraction reveals a planar TETOR conformation (versus highly twisted diester bithiophene), showing distinctive advantages of incorporating alkoxy on promoting backbone planarity. Compared to first-generation 3-alkyl-3′-alkoxy-2,2′-bithiophene (TRTOR), TETOR contains an additional planarizing (thienyl)­S···O­(carbonyl) interaction. Consequently, TETOR-based polymer (TffBT-TETOR) has greatly lower-lying FMOs, stronger aggregation, closer π-stacking, and better miscibility with fullerenes versus the TRTOR-based counterpart (TffBT-TRTOR). These characteristics are attributed to the additional S···O interaction and electron-withdrawing ester substituent, which enhances backbone planarity, charge transport, and PSC performance. Thus, TffBT-TETOR-based PSCs exhibit an increased PCE of 10.08%, a larger V oc of 0.76 V, and a higher J sc of 18.30 mA cm–2 than the TffBT-TRTOR-based PSCs. These results demonstrate that optimizing intramolecular noncovalent S···O interactions by incorporating electron-withdrawing ester groups is a powerful strategy for materials invention in organic electronics.