Flexible photodetectors (PDs) are attracting more attention due to their promising applications in wearable optoelectronic devices, bendable imaging sensors, and implantable optoelectronics. For the easy‐processable technology of massively fabricating PDs, instead of the expensive and complex high‐vacuum technique, the well‐matched work function of their active materials is essential. Herein, all‐sprayed‐processable and large‐area PDs are demonstrated on common paper based on two‐dimensional (2D) CsPbBr3 nanosheets and conductive Ti3C2Tx (MXene). Ascribed to the superior conductivity of MXene, high crystallinity of 2D CsPbBr3, and their well‐matched work function, the as‐prepared PDs exhibit an outstanding on/off current ratio up to 2.3 × 103 and a remarkable photoresponse as fast as 18 ms. Specifically, the detectivity (D*) of 6.4 × 108 Jones and responsivity (R) of 44.9 mA W−1 under a bias of 10 V are achieved. Besides, after bending 1500 cycles, the as‐prepared PDs can still maintain the excellent flexibility and stability. Based on this, a superior‐quality and large‐area 1665 pixel sensor in 72 cm2 (≈24 units cm−2) is developed, and it can clearly transmit the image of “0” to realize the photocommunication function. This work provides a low‐cost method of massively producing the flexible large‐area PDs for wearable optoelectronic devices and expanded photocommunication.

Azafullerenes derived from nitrogen substitution of carbon cage atoms render direct modifications of the cage skeleton, electronic, and physicochemical properties of fullerene. Gas-phase ionized monometallic endohedral azafullerene (MEAF) [La@C81N]+ formed via fragmentation of a La@C82 monoadduct was detected in 1999, but the pristine MEAF has never been synthesized. Here, we report the synthesis, isolation, and characterization of the first pristine MEAF La@C81N, tackling the two-decade challenge. Single-crystal X-ray diffraction study reveals that La@C81N has an 82-atom cage with a pseudo C 3v (8) symmetry. According to DFT computations, the nitrogen substitution site within the C82 cage is proposed to locate at a hexagon/hexagon/pentagon junction far away from the encapsulated La atom. La@C81N exists in stable monomer form with a closed-shell electronic state, which is drastically different from the open-shell electronic state of the original La@C82. Our breakthrough in synthesizing a new type of azafullerene offers a new insight into the skeletal modification of fullerenes.

The manipulation of microstructure from the growth stage is desired in perovskite materials to improve the environmental stability and enhance the perovskite‐based device performance. Herein, the traditional challenges of self‐assembly of multifunctional perovskite nano/microwires (MWs) are overcome by developing a new nanocrystal strategy to intelligently build self‐inlaid jagged CsPbBr3 MWs for photodetectors (PDs) with a combination of improved light‐harvesting capability, heat dissipation, and humidity stability. With a collection of compelling features, the as‐constructed PDs deliver an ultralow dark current of 10−12 A, excellent response speed of 26 ms, superior detectivity (D*) of 1.9 × 1012 Jones, and peak external quantum efficiency of 939%. Furthermore, attributing to the interlocking–protecting effect of the self‐inlaid monocrystalline CsPbBr3 nanostructure, the CsPbBr3 MW PDs display improved stability against heat and humidity with promoted heat dissipation ability at 60 °C and 97% photocurrent retention under 80% humidity treatment for 200 min, respectively. This work represents a significant advancement in developing high‐performance and environmentally stable PDs.