The heterointerface between organic and inorganic semiconductors widely presents in organic optoelectronics, especially for polymer solar cells (PSCs). [1][2][3] Ideally, to facilitate the charge extraction (or injection) at such heterojunction, it requires the presence of not only the minimized interfacial energy barriers between these two composition-different semiconductors, but also the enlargement of build-in field across the interfaces. [4,5] Within a few years, recently, the fast evolution of organic active components, particularly from fullerene to nonfullerene acceptors, has enabled rapid progresses of power conversion efficiencies (PCEs) for PSCs. [6][7][8][9][10][11][12][13][14][15][16][17] Notably, a number of optimal active layers can already achieve near 100% internal quantum efficiencies (IQEs) for the conversion of absorbed photons into photogenerated carriers. [6,18] Therefore, in such devices, the heterointerface governing charge extraction (or injection) becomes deterministic factors to affect the overall performance as well as stability of PSCs.For examples, among the high-performance PSCs, inverted ones have routinely employed metal oxides, such as ZnO and titanium oxide (TiO 2 ) as electron-transport layers (ETLs), [19,20] which have been paired with a large range of organic-active components with variable energetics and surface energies. One therefore can easily identify those conventional metal oxide ETLs; once employed for fullerene, PSCs should present significant mismatch to nowadays nonfullerene acceptors. [21][22][23][24] The mismatched energy levels between metal oxide and organic photoactive layers can create contact resistances to hinder charge extraction. [25] Besides, chemical and physic defects of metal oxides, such as dangling hydroxide (OH) or Zn vacancy on the surface or crystal boundary of ZnO, could trap charges to cause carrier recombination loss. [26] Moreover, the photocatalytic activities of semiconducting metal oxides should also pose significant impacts toward the contacted organic semiconductors. It has been known that ZnO and TiO 2 could generate reactive species upon excitation, such as hydroxide radical and superoxide radical anion in ambient, to degrade vulnerable organic semiconductors with active hydrogen and double bonds. [27] These interfacial issues not only hinder charge events at the heterointerface, Charge events across organic-metal oxide heterointerfaces routinely occur in organic electronics, yet strongly influence their overall performance and stability. They become even more complicated and challenging for the heterojunction conditions in polymer solar cells (PSCs), especially when nonfullerene acceptors with varied energetics are employed. In this work, an effective interfacial strategy that utilizes novel small molecule self-assembled monolayers (SAMs) is developed to improve the electronic and electric, as well as chemical properties of organic-zinc oxide (ZnO) interfaces for nonfullerene PSCs. It is revealed that the tailored SAMs with well-cont...

Center (NPVM) with the aperture area of 19.30 cm 2 ; The numbers in parentheses represent the average parameters for 10 modules.

Despite the remarkable progress achieved in recent years,o rganic photovoltaics (OPVs) still need work to approach the delicate balance between efficiency,s tability, and cost. Herein, two fully non-fused electron acceptors, PTB4F and PTB4Cl, are developed via at wo-step synthesis from single aromatic units.T he introduction of at wo-dimensional chain and halogenated terminals for these non-fused acceptors playsasynergistic role in optimizing their solid stacking and orientation, thus promoting an elongated exciton lifetime and fast charge-transfer rate in bulk heterojunction blends.A saresult, PTB4Cl, upon blending with PBDB-TF polymer,h as enabled single-junction OPVs with power conversion efficiencies of 12.76 %, representing the highest values among the reported fully unfused electron acceptors so far.

The fast degradation of the charge‐extraction interface at indium tin oxide (ITO) poses a significant obstacle to achieving long‐term stability for organic solar cells (OSCs). Herein, a sustainable approach for recycling non‐sustainable indium to construct efficient and stable OSCs and scale‐up modules is developed. It is revealed that the recovered indium chloride (InCl3) from indium oxide waste can be applied as an effective hole‐selective interfacial layer for the ITO electrode (noted as InCl3–ITO anode) through simple aqueous fabrication, facilitating not only energy level alignment to photoactive blends but also mitigating parasitic absorption and charge recombination losses of the corresponding OSCs. As a result, OSCs and modules consisting of InCl3–ITO anodes achieve remarkable power conversion efficiencies (PCEs) of 18.92% and 15.20% (active area of 18.73 cm2), respectively. More importantly, the InCl3–ITO anode can significantly extend the thermal stability of derived OSCs, with an extrapolated T80 lifetime of ≈10 000 h.