Hole‐transporting materials (HTMs) play a critical role in realizing efficient and stable perovskite solar cells (PVSCs). Considering their capability of enabling PVSCs with good device reproducibility and long‐term stability, high‐performance dopant‐free small‐molecule HTMs (SM‐HTMs) are greatly desired. However, such dopant‐free SM‐HTMs are highly elusive, limiting the current record efficiencies of inverted PVSCs to around 19%. Here, two novel donor–acceptor‐type SM‐HTMs (MPA‐BTI and MPA‐BTTI) are devised, which synergistically integrate several design principles for high‐performance HTMs, and exhibit comparable optoelectronic properties but distinct molecular configuration and film properties. Consequently, the dopant‐free MPA‐BTTI‐based inverted PVSCs achieve a remarkable efficiency of 21.17% with negligible hysteresis and superior thermal stability and long‐term stability under illumination, which breaks the long‐time standing bottleneck in the development of dopant‐free SM‐HTMs for highly efficient inverted PVSCs. Such a breakthrough is attributed to the well‐aligned energy levels, appropriate hole mobility, and most importantly, the excellent film morphology of the MPA‐BTTI. The results underscore the effectiveness of the design tactics, providing a new avenue for developing high‐performance dopant‐free SM‐HTMs in PVSCs.

Grain boundaries in lead halide perovskite films lead to increased recombination losses and decreased device stability under illumination due to defect‐mediated ion migration. The effect of a conjugated polymer additive, poly(bithiophene imide) (PBTI), is investigated in the antisolvent treatment step in the perovskite film deposition by comprehensive characterization of perovskite film properties and the performance of inverted planar perovskite solar cells (PSCs). PBTI is found to be incorporated within grain boundaries, which results in an improvement in perovskite film crystallinity and reduced defects. The successful defect passivation by PBTI yields reduces recombination losses and consequently increases power conversion efficiency (PCE). In addition, it gives rise to improved photoluminescence stability and improved PSC stability under illumination which can be attributed to reduced ion migration. The optimal devices exhibit a PCE of 20.67% compared to 18.89% of control devices without PBTI, while they retain over 70% of the initial efficiency after 600 h under 1 sun illumination compared to 56% for the control devices.

High performance flexible polymer solar cells are realized by using the 3D printer-based slot die coating method.

processing at low cost compared with their inorganic counterparts. The first breakthrough in OPV technology was achieved by realizing BHJ active layers with nanoscale bicontinuous network structures of electron donor (D) and acceptor (A) materials; this structure enables efficient exciton separation at the D-A interface. [1] The development of push-pull-type donor polymers has effectively extended the light absorption range of OPVs into the near-infrared (NIR) region, which has ultimately led to substantial improvements in power conversion efficiency (PCE) to greater than 10%. In particular, highly crystalline donor polymers such as PffBT4T-2OD substantially improved charge-transport properties, enabling OPV devices with a BHJ film thickness greater than 200 nm to operate. [2] Historically, fullerene derivatives have been dominantly used as acceptors in OPVs because of their excellent electron-accepting and transporting properties and because they can be prepared with a morphology optimized for efficient charge-carrier generation and transport. [3,4] However, despite such promising characteristics, OPVs based on fullerene derivatives have drawbacks of limited light-absorption properties, poor energylevel tunability, and poor morphological and/or photochemical stability. [5,6] Over the past several years, tremendous efforts have been directed toward the development of nonfullerenebased OPVs to overcome these limitations. The advantages of nonfullerene acceptors over fullerenes include easily tunable energy levels, which enables OPVs to achieve substantially higher open-circuit voltages (V OC s) than conventional fullerenebased devices. [7] In addition, nonfullerene acceptors enable better light absorption properties and therefore generate higher photocurrents than fullerene derivatives. [8] Furthermore, nonfullerene acceptors with appropriate molecular tailoring can provide chemically stable photoactive materials, potentially enhancing long-term device stability. [5] Recent breakthroughs realized through the development of small molecular nonfullerene acceptors have resulted in remarkable enhancements in the PCEs of single-junction OPVs to greater than 17%, which demonstrates the potential for the large-scale manufacture of OPVs. [9] When translating photovoltaic technology from laboratory to commercial products, low cost, high PCE, and high Organic solar cells based on bulk heterojunctions (BHJs) are attractive energy-conversion devices that can generate electricity from absorbed sunlight by dissociating excitons and collecting charge carriers. Recent breakthroughs attained by development of nonfullerene acceptors result in significant enhancement in power conversion efficiency (PCEs) exceeding 17%. However, most of researches have focused on pursuing high efficiency of small-area (<1 cm 2) unit cells fabricated usually with spin coating. For practical application of organic photovoltaics (OPVs) from lab-scale unit cells to industrial products, it is essential to develop efficient technologies that can extend act...

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.